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EP4665738A1 - Mixed p,n-donor ligands, their complexes and use thereof - Google Patents

Mixed p,n-donor ligands, their complexes and use thereof

Info

Publication number
EP4665738A1
EP4665738A1 EP24703511.6A EP24703511A EP4665738A1 EP 4665738 A1 EP4665738 A1 EP 4665738A1 EP 24703511 A EP24703511 A EP 24703511A EP 4665738 A1 EP4665738 A1 EP 4665738A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
aryl
substituted
jcp
ligand
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24703511.6A
Other languages
German (de)
French (fr)
Inventor
Viktoria Daeschlein-Gessner
Julian LÖFFLER
Nicolas KAISER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Umicore AG and Co KG
Original Assignee
Umicore AG and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Umicore AG and Co KG filed Critical Umicore AG and Co KG
Publication of EP4665738A1 publication Critical patent/EP4665738A1/en
Pending legal-status Critical Current

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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/59—Hydrogenated pyridine rings
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
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    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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    • C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
    • C07F9/65848—Cyclic amide derivatives of acids of phosphorus, in which two nitrogen atoms belong to the ring
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    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/50—Non-coordinating groups comprising phosphorus
    • B01J2540/54—Quaternary phosphonium groups

Definitions

  • WO 2019/030304 shows the use of novel ligands to prepare metal complexes and their use in organometallic catalysis.
  • a new type of ligands containing nitrogen and phosphorous has been found that surprisingly can form new, previously unknown and catalytically active metal complexes, in particular transition metal compounds.
  • the invention also relates to metal complexes, in particular transition metal and precious metal complexes, comprising at least one ligand of formula 1.
  • the invention also relates to a method for carrying coupling reactions involv- ing such complexes, which might be isolated before use in a coupling reaction or which might be used in a one-pot reaction without isolation of such com- plexes.
  • the respective ligands of the invention and com- plexes comprising such ligands are effective to enable coupling reactions.
  • Variation range Due to the greater range of easy-to-prepare aminophos- phanes from PCl3 and simple amines, it is easier to generate a broader spec- trum of ligands of formula 1 than with alkyl and aryl substituents. This allows easier control of the steric properties and binding ability of the nitrogen.
  • a ligand of formula 1, Formula 1 wherein R1 is alkyl, perfluoroalkyl, aryl or cycloalkyl, each substituted or unsubstituted, cyano, sulfonyl -SO2-R10 with R10 C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each unsubstituted or substituted with C1-C4 alkyl or C1-C4 perfluoroalkyl; silyl -Si(R20R30R40) with R20, R30 and R40, independently from each other being C1-C6-alkyl or C5-C10 aryl, each unsubstituted or substituted with C1-C4 alkyl; R2 is alkyl, cycloalkyl, adamantyl or aryl, each substituted or unsub- stituted; R3, R4 and R5 is alkyl, cycloal
  • a ligand of item 1, wherein R1 is selected from C1 to C9 alkyl, C4-C8 cycloalkyl, C5-C10 aryl, cyano, sulphonyl -SO2-R10 where R10 C1- C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each unsubstituted or substi- tuted by one or more C1 to C4 alkyl, C1 to C4 alkoxy or C1 to C4 per- fluoroalkyl; silyl -Si(R20R30R40) where R20, R30 and R40, each of which is independently C1-C6 alkyl or C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl, or R1 is C5-C10 aryl which may be substituted one or more times by C1 to C5 alkyl, C1 to C5 alkoxy or C1 to
  • R3, R4 and R5 are, independently from each other, C1 to C5 alkyl, C4-C8 cycloal- kyl, adamantyl, C5 to C6 aryl, which can be unsubstituted or substi- tuted with C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or at least two of R3, R4 and R5 are a C2 to C5 alkyl, C2 to C5 alkenyl or C2 to C4 alkylether bridge and together with the phosphorus atom, are forming a heterocyclic ring. 6.
  • R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or, individually or collectively are forming a hetero- cyclic ring with R3, R4 or R5 and the nitrogen atom they are connected to.
  • a ligand according to any of the preceding items, wherein R3 and R6 and/or R4 and R7 and/or R5 and R8, taken together are a C2 to C8 al- kyl or C2 to C8 alkylether bridge, optionally substituted with one or more C1 to C5 groups or the C2 to C8 alkyl or C2 to C8 alkylether bridge being part of a fused C4 to C8 cycloalkyl ring, taken together with the nitrogen atom they are connected to, are forming a heterocy-root ring.
  • R1 is se- lected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert.
  • R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl; at least two of of m, n and o are 1; at least two of R3, R4 and R5 together are a C2 to C8 alkyl or C2 to C8 alkylether bridge, optionally substituted with one or more C1 to C5 al- kyl or cycloalkyl groups; or the C2 to C8 alkyl or C2 to C8 alkylether bridge being part of a fused C4 to C8 cycloalkyl ring,
  • R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl, sulphonyl -SO2-R10
  • R10 C5-C10 aryl, which is unsubstituted or substituted by C1 to C4 alkyl
  • R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl
  • R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4- C8 cycloalkyl, adamantyl, C5 to C10 aryl
  • R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl
  • R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl;
  • R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl;
  • m is 0, n and o are 1
  • R3 is C4-C8 cycloalkyl or adamantyl;
  • R4 and R5 together are a C2 to C8 alkyl or C2 to C8 alkylether bridge forming a heterocyclic ring with the phosphorous atom, said C2 to C8 alkyl or C2 to C8 alkylether bridge optionally substituted with one or more C1 to C5 alkyl groups; or the C2 to C8 alkyl or C2 to C8 al- kylether bridge entirely or partially being part of a fused C4 to C8 cy- cloalkyl ring
  • R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl
  • R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl
  • m, n and o are 1
  • R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4- C8 cycloalkyl or C5 to C10 aryl
  • R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl.
  • R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl;
  • R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl;
  • m, n and o are 1;
  • R3 and R6, R4 and R7, R5 and R8, each of the pairs taken together are a C2 to C8 alkyl bridge or C2 to C8 alkylether bridge, optionally said C2 to C8 alkyl bridge may be partially or entirely part of a fused C4 to C8 cycloalkyl ring.
  • R3, R4 and R5 is methyl, phenyl, mesityl, 24.
  • a metal complex comprising a transition metal and a ligand of any of items 1 to 26 and optionally comprising at least one organic ligand L and/or at least one halogen X. 28.
  • the organic lig- ands are selected from the group consisting of dibenzylidenacetone (DBA), acetylacetone (acac), p-tolyl, m-tolyl, o-tolyl, cyclooctadiene (COD) and carbon monoxide.
  • a method for carrying out a coupling reaction comprising the steps of - providing a reaction mixture comprising at least a substrate, a cou- pling partner and a metal complex comprising a ligand according to any one of items 1 to 26; and - reacting the substrate with the coupling partner in the presence of the metal complex or its derivative to form a coupling product.
  • the metal complex comprising a ligand is a metal complex ac- cording to any one of items 27 to 31.
  • the method according to item 34 wherein the substituted aromatic compound is an aromatic or heteroaromatic compound.
  • 36. The method according to item 34 or 35, wherein the substituted aro- matic compound is substituted with a leaving group and/or an unsatu- rated aliphatic group or a leaving group.
  • 37. The method according to item 36, wherein the leaving group is se- lected from the group consisting of halogen, triflate, tosylate, nosylate and mesylate, and/or the unsaturated aliphatic group is selected from the group consisting of alkene or alkyne, in particular with 2 to 12, in particular with 2 to 8 carbon atoms. 38.
  • the coupling partner is an organometallic compound.
  • the organometallic com- pound is selected from the group consisting of organic boron com- pounds, organolithium compounds, organozinc compounds, organolith- ium compounds, organosodium compounds, organopotassium com- pounds and Grignard compounds.
  • the organometallic compound contains at least one aromatic group.
  • the organometallic compound contains at least one unsaturated aliphatic group. 42.
  • the organometallic compound contains at least one saturated aliphatic group.
  • the coupling reaction can be selected from the group consisting of (i) catalytic hydrofunctionalization reactions of alkynes and alkenes; (ii) catalytic hydroamination reactions of alkynes and alkenes; (iii) catalytic O-H addition reactions on alkynes and alkenes; (iv) catalytic coupling reactions; (v) catalytic Kumada coupling reactions, Murahashi coupling reac- tions, Negishi coupling reactions, or Suzuki coupling reactions, espe- cially for the production of biarylene; (vi) catalytic cross-coupling reactions, in particular C-N and C-O cou- pling reactions; and/or (vii) catalytic Heck coupling reactions, in particular for the prepara- tion of arylated olefins, and Sonogashira
  • R1 represents C1 to C9 alkyl, C4-C8 cycloalkyl, C5-C10 aryl, which aryl can be unsubstituted or substituted with C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl. More specifically, R1 is selected from methyl, ethyl, propyl, isopropyl, n-bu- tyl, sec-butyl, tert.
  • ligands of formula 1 generally is R2 C1 to C9 alkyl, C4-C8 cycloalkyl, adamantyl, C5 to C10 aryl, which can be unsubstituted or substi- tuted with one or more C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 per- fluoroalkyl.
  • R2 is selected from methyl, ethyl, propyl, isopropyl, n-bu- tyl, sec-butyl, tert. butyl, n-pentyl, n-pentyl (amyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (iso-pentyl or iso-amyl), 3-methyl- but-2-yl, 2-methylbut-2-yl, 2, 2-dimethylpropyl (neopentyl), n-hexyl, tri- fluoromethyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adaman- tyl, phenyl, o-, m-, or p-methylphenyl, naphthyl.
  • R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4-C8 cycloalkyl, adamantyl, 1-adamantyl, 2-adamantyl, C5 to C10 aryl, which can be unsubstituted or substituted with C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl.
  • at least two of R3, R4 and R5 are a C2 to C10 alkyl, C2 to C10 alkenyl or C2 to C10 alkylether bridge and to- gether with the phosphorus atom, are forming a heterocyclic ring.
  • R3 can be a methyl or cyclohexyl ring directly linked to the phosphorous atom when m is 0 (zero)
  • R4 and R5 to- gether could be a C2 alkenyl bridge or a C3 alkyl bridge and with n and o being 1 would form a five-membered unsaturated ring consisting of P, two substituted nitrogen atoms, both linked with the C2 alkenyl bridge or a six- membered saturated ring consisting of P, two substituted nitrogen atoms, both linked with the C3 alkyl bridge.
  • R3, R4 and R5 are, independently from each other, C1 to C5 alkyl, C4-C8 cycloalkyl, adamantyl, 1-adamantyl, 2-adamantyl, C5 to C6 aryl, which can be unsubstituted or substituted with C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or at least two of R3, R4 and R5 are a C2 to C5 alkyl, C2 to C5 alkenyl or C2 to C4 alkylether bridge and together with the phosphorus atom, are forming a heterocyclic ring.
  • At least two of R3, R4 and R5 together are a C2 to C8 alkyl or C2 to C8 alkylether bridge, optionally substituted with one or more C1 to C5 alkyl or cycloalkyl groups; or the C2 to C8 alkyl or C2 to C8 alkylether bridge being part of a fused C4 to C8 cycloalkyl ring, forming a heterocyclic ring with the phosphorous atom.
  • R3 can be a methyl or cyclohexyl ring directly linked to the phosphorous atom when m is 0 (zero)
  • R4 and R5 to- gether could be a 1,2-cyclohexyl bridge and with n and o being 1 would form a five-membered unsaturated ring consisting of P, two substituted ni- trogen atoms, each connected to the 1- and 2-position of the cyclohexyl ring providing a C2 alkyl bridge so that the heterocyclic five-membered ring is fused with a cyclohexyl ring.
  • R6, R7 and R8 are, independently of each other, C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or, R6, R7 and R8 are individually or collectively are forming a heterocyclic ring with R3, R4 or R5 and the nitrogen atom they are connected to.
  • R3 and R6 and/or R4 and R7 and/or R5 and R8, taken together are a C2 to C8 alkyl or C2 to C8 alkylether bridge, op- tionally substituted with one or more C1 to C5 groups or the C2 to C8 alkyl or C2 to C8 alkylether bridge being part of a fused C4 to C8 cycloalkyl ring, taken together with the nitrogen atom they are connected to, are forming a heterocyclic ring.
  • R3 and R6 together may form, for example, an aziridine ring pyrrolidine ring or piperidine ring, or in the case of an alkylether bridge, for example an oxaziridine ring, an oxazolidine ring, an isoxazolidine ring or morpholine ring.
  • R3, R4, R5, R6, R7 and R8, independently of each other, are selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl butyl, n-pentyl, n-pentyl (amyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (iso-pentyl or iso-amyl), 3-methyl- but-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, cyclo- butyl, cyclopentyl, cyclohexyl, phenyl, mesity
  • At least one of m, n and o must be 1.
  • it is possible for at least two of m, n and o are 1. In some embodiments if is also possible for a ligand that all of m, n and o are 1.
  • R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl, sulphonyl -SO2-R10
  • R10 C5-C10 aryl, which is unsub- stituted or substituted by C1 to C4 alkyl
  • R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl, which may be 1-ada- mantyl or 2-adamantyl
  • at least two of m, n and o are 1
  • at least two of R3, R4 or R5 together are a C2 to C8 alkyl or C2 to C8 al- kylether bridge, optionally substituted with one or more C1 to C5 alkyl or cycloalkyl groups
  • the C2 to C8 alkyl or C2 to C8 alkylether bridge being part of
  • R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl, sulphonyl -SO2-R10
  • R10 C5-C10 aryl, which is unsub- stituted or substituted by C1 to C4 alkyl
  • R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl, which may be 1-ada- mantyl or 2-adamantyl
  • R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4-C8 cycloalkyl, adamantyl, which may be 1-adamantyl or 2-adamantyl, C5 to C10 aryl
  • R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted
  • R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl;
  • R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl, which may be 1-ada- mantyl or 2-adamantyl;
  • m is 0, n and o are 1
  • R3 is C4-C8 cycloalkyl or adamantyl, which may be 1-adamantyl or 2-ada- mantyl;
  • R4 and R5 together are a C2 to C8 alkyl or C2 to C8 alkylether bridge form- ing a heterocyclic ring with the phosphorous atom, said C2 to C8 alkyl or C2 to C8 alkylether bridge optionally substituted with one or more C1 to C5 al- kyl groups; or the C2 to C8
  • a further embodiment relates to ligands wherein R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl, which may be 1-ada- mantyl or 2-adamantyl; m, n and o are 1; and R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4-C8 cycloalkyl or C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl.
  • a ligand contains the substituents
  • R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl
  • R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl, which may be 1-ada- mantyl or 2-adamantyl
  • m, n and o are 1
  • R3 and R6, R4 and R7, R5 and R8, each of the pairs taken together are a C2 to C8 alkyl bridge or C2 to C8 alkylether bridge, optionally said C2 to C8 al- kyl bridge may be partially or entirely part of a fused C4 to C8 cycloalkyl ring.
  • R1 is selected from methyl, isopropyl, phenyl and o-tolyl.
  • R2 is selected from methyl, isopropyl, tert.-butyl, cyclohexyl, phenyl and adamantyl, which may be 1-adamantyl or 2-adamantyl.
  • R3, R4 and R5 are selected from methyl, phenyl, mesityl.
  • one or more of R6, R7 and R8 is methyl, isopropyl, isopentyl, neopentyl, phenyl, mesityl.
  • R3 and R6 and/or R4 and R7 and/or R5 and R8, taken together with the nitro- gen atom they are connected to, are forming a piperidinyl or morpholinyl ring.
  • a ligand according to any of the preceding items, wherein R3 with R6 and R4 with R7 and R5 with R8, taken together with the nitrogen atom they are connected to, are forming a piperidinyl or morpholinyl ring and conse- quently, all of m, n and o are equal to 1.
  • the ligands described above are capable of forming metal complexes.
  • the subject invention also relates to metal complexes comprising a metal, a ligand of formula 1 and optionally comprising at least one organic ligand L and/or at least one halogen X. More specifically, the subject invention also relates to transition metal com- plexes comprising a transition metal and a ligand of formula 1 and option- ally comprising at least one organic ligand L and/or at least one halogen X. Even more specifically, the transition metal is a precious metal.
  • the transition metal is selected from the group consisting of ruthenium, os- mium, rhodium, nickel, iridium, palladium, platinum, silver and gold, in par- ticularly selected from the group consisting of rhodium, iridium, palladium and gold.
  • the organic ligands can be selected from the group consisting of dibenzylidenacetone (DBA), acetylacetone (acac), p-tolyl, m-tolyl, o-tolyl, cyclooctadiene (COD) and carbon monoxide.
  • the halogen X is chlorine or bromine.
  • the Invention also relates to a method for carrying out a coupling reaction employing a ligand as described above, which preferably is present in a metal complex, in particular a metal complex as described above. More specifically, the invention also relates to a method for carrying out a coupling reaction comprising the steps of - providing a reaction mixture comprising at least a substrate, a cou- pling partner and a metal complex comprising a ligand as described above, particularly the ligand according to any one of items 1 to 26 above; and - reacting the substrate with the coupling partner in the presence of the metal complex or its derivative to form a coupling product.
  • the metal complex com- prising a ligand is a metal complex as described above, in particular as de- fined in any one of items 27 to 31 above.
  • the substrate can be a substituted unsaturated or substituted aromatic compound, in particular the substituted aromatic compound can be an aro- matic or heteroaromatic compound.
  • the substrate can be substituted, among others, with a leaving group or an unsaturated aliphatic group, whereby it has shown to be useful if the leav- ing group is selected from the group consisting of halogen, in particular Cl, Br or I (chlorine, bromine, iodine), triflate, tosylate, nosylate and mesylate and/or the unsaturated aliphatic group is selected from the group consisting of alkene, or alkyne, in particular with 2 to 12, especially 2 to 8 carbon at- oms.
  • halogen in particular Cl, Br or I (chlorine, bromine, iodine)
  • triflate tosylate, nosylate and mesylate
  • the unsaturated aliphatic group is selected from the group consisting of alkene, or alkyne, in particular with 2 to 12, especially 2 to 8 carbon at- oms.
  • the coupling partner may comprise an organometallic compound, which in particular can be selected from the group consisting of organic boron com- pounds, organic lithium compounds, organic zinc compounds, organic lith- ium compounds and Grignard compounds, wherein advantageously the or- ganometallic compound comprises at least one aromatic group, or wherein the organometallic compound comprises at least one unsaturated aliphatic group, or wherein the organometallic compound comprises at least one sat- urated aliphatic group.
  • organometallic compound which in particular can be selected from the group consisting of organic boron com- pounds, organic lithium compounds, organic zinc compounds, organic lith- ium compounds and Grignard compounds, wherein advantageously the or- ganometallic compound comprises at least one aromatic group, or wherein the organometallic compound comprises at least one unsaturated aliphatic group, or wherein the organometallic compound comprises at least one sat- urated aliphatic group.
  • the coupling reaction can be selected from the group consisting of (i) catalytic hydrofunctionalization reactions of alkynes and alkenes; (ii) catalytic hydroamination reactions of alkynes and alkenes; (iii) catalytic O-H addition reactions on alkynes and alkenes; (iv) catalytic coupling reactions; (v) catalytic Kumada coupling reactions, Murahashi coupling reactions, Negishi coupling reactions, or Suzuki coupling reactions, especially for the production of biarylene; (vi) catalytic cross-coupling reactions, in particular C-N and C-O coupling reactions; and/or (vii) catalytic Heck coupling reactions, in particular for the preparation of ar- ylated olefins, and Sonogashira coupling reactions, in particular for the preparation of arylated and alkenylated alkynes.
  • catalytic ⁇ -arylations of carbonyl compounds and imines More specifically, the ligands and their transition metal complexes, in partic- ular their palladium complexes, are particularly useful for the catalytic ⁇ -ar- ylations of carbonyl compounds and imines, specifically carbonyl compounds and more specifically ketones. They have been found to be particularly use- ful in the arylation of acetone.
  • ligands of Formula 2 have been found to be particularly useful: Formula 2 wherein A is methyl or o-tolyl, B is cyclohexyl or isopropyl and C is piperidyl or morpholyl, both bound to the P atom via their ring nitrogen atom, such as compounds wherein A, B and C are defined as in the following table: No.
  • These ligands are used in transition metal complexes as defined above. The invention is explained in more detail in the following examples.
  • Phospho- rous trichloride (8.11 g, 5.17 ml, 59.1 mmol) was added drop- wise and the colorless suspension was stirred at room temperature overnight. The solid was filtered off, extracted with Et2O (3 x 50 ml) and all volatiles were removed in vacuo to obtain a yellow oil. The compound was redissolved in Et2O (150 ml) and cooled to 0 °C. CyMgCl (1.35 M in Et2O, 39.8 ml, 53.7 mmol) was added slowly and the suspension was allowed to warm up to room temperature overnight. The solid was filtered off, extracted with Et 2 O (3 x 50 ml) and the solvent was removed in vacuo.
  • Dimesitylethane-1,2-diamine (7.71 g, 26.0 mmol) and (6.61 g, 9.18 ml, 65.0 mmol) were dissolved in (120 ml) and cooled to 0 °C.
  • CyPCl 2 (4.82 g, 4.00 ml, mmol) was added dropwise and the mixture was refluxed for 4 d.
  • the solvent of the yellow mixture was removed in vacuo and the residue was extracted with THF (3 x 70 ml).
  • the solvent of the filtrate was removed in vacuo and the residue was washed with Et2O (3 x 5 ml).
  • the crude product was dissolved in hot Et2O (100 ml), was filtered and slowly cooled to -30 °C.
  • Colorless crystals were formed that, were filtered off and were washed with cold Et2O (3 x 10 ml). The product was obtained as color- less crystals in approximately 95% purity according to 31 P ⁇ 1 H ⁇ NMR spectroscopy and was used without further purification. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by re- crystallisation from hot Et 2 O. Yield: (3.89 g, 9.52 mmol, 37%).
  • N-Methylaniline (17.2 g, 17.5 ml, 160 mmol) and triethylamine (18.6 g, 25.8 ml, 183 mmol) were dissolved in toluene (200 ml) at 0 °C.
  • Phosphorous trichloride (6.28 g, 4.00 ml, 45.7 mmol) was added slowly and the resulting suspension was warmed up to room tem- perature overnight.
  • the solid was filtered off and extracted with hot toluene (3 x 200 ml). The solvent was removed in vacuo to obtain an orange slimy residue, that was washed with Et 2 O (3 x 50 ml).
  • 3 ⁇ H 2 was obtained as a colorless solid (5.4 g, 14.54 mmol, 73%). 3 ⁇ H 2 was used without further purification.
  • Cyclohexyldichlorophosphine (29.2 mmol, 1 eq.) and 12.4 (87.6 mmol, 3 eq.) were dissolved in 50 ml and cooled to 0 °C.
  • a solution of 3.24 ml N,N- dimetzhylethane-1,2-diamine (29.2 mmol, 1 eq.) in 70 ml dieth- ylether was prepared and slowly added via an addition funnel at 0 °C over the period of 1h. During the addition a colorless solid precipitated.
  • CHNS Calculated: C: 48.82, H: 8.41, N: 8.99. Measured: C: 48.82, H: 8.49, N: 8.74. Melting point: 195.5 °C.
  • the colorless solid was filtered off and was washed with toluene (3 x 20 ml) and pentane (3 x 20 ml).
  • the phosphonium salt 11 ⁇ H2 was obtained as a colorless solid.
  • Colorless crystals suitable single crystal X-ray diffraction experiments were obtained by slow vapor diffusion of pentane into a saturated THF solution of the compound. Yield: (12.7 g, 25.9 mmol, 95%).
  • the phosphonium salt 12 ⁇ H2 was ob- tained as a colorless solid after drying at 140 °C in vacuo for 10 h. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by recrystallisation from hot toluene. Yield: (3.86 g, 7.08 mmol, 50%).
  • the solution was stirred for 45 min and then 2.67 ml of dicyclohexylchlorophosphine (12.1 mmol, 1 eq.) were added at room temperature. A colorless solid precipitated shortly after addition.
  • the suspension was stirred for 2 h and then 7.8 ml of a n-BuLi solution (1.55 M in hexane, 12.1 mmol, 1 eq.) were slowly added until a clear, yellow solution was formed.
  • the solution was stirred for 30 min and the sol- vent was subsequently removed in vacuuo. The residue was suspended in 50 ml acetonitrile and stirred overnight, forming a colorless solid.
  • Phosphonium salt 5 ⁇ H2 was suspended ml THF and deprotonated by slow addition of 1.38 ml of a n-BuLi solution (1.55 M in hexane, 2.14 mmol, 1 eq.) until a clear, slightly yellow solution was formed. The solution was stirred for 45 min and then 0.47 ml of dicyclohexylchlorophosphine (2.14 mmol, 1 eq.) were added at room temperature. A colorless solid precipitated shortly after addi- tion.
  • Phosphonium salt 7 ⁇ H 2 was sus- pended in 20 ml THF and deprotonated by slow addition of 3.88 ml of a n-BuLi solution (1.6 M in hexane, 5.82 mmol, 1 eq.) until a clear, slightly yellow solution was formed. The so- lution was stirred for 45 min and then 1.02 ml of diisopropyliodophosphine (6.4 mmol, 1.1 eq.) were added at room temperature. A colorless solid pre- cipitated shortly after addition.
  • Phosphine L12 was synthesized from 12 ⁇ H2 (8.23 g, 15.1 mmol) according to the general procedure for P,N- YPhos ligands. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow evap- oration of a saturated hexane solution. Yield: (7.51 g, 12.25 mmol, 81%). NMR spectroscopy was performed at 70 °C.
  • L15 was synthesized from 15 ⁇ H 2 (6.51 g, mmol) according to the general procedure for P,N- ligands, with the exception that the phosphonium was deprotonated in toluene. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow evap- oration of a saturated hexane solution. Yield: (4.93 mg, 8.88 mmol, 66%). NMR spectroscopy was performed at 70 °C. NMR spectral assignment in some cases was not possible due to overlapping peaks from the three different cyclohexyl moieties.
  • the vial was taken outside of the glovebox and 4 ml of tetrahydro- furan, 0.118 ml (1 mmol, 1 eq.) of 4-chlorotoluene, 0.259 ml tetradecane (1 mmol, 1 eq.) and 1.1 mmol (1.1 eq.) of the amine were added via syringe.
  • a second vial was charged with an equimolar amount of the free ligand and tris(dibenzylideneacetone)dipalladium(0).
  • the catalyst was allowed to pre- form in 0.5 ml of THF and stirred for 30 minutes. The catalyst solution was added to the reaction mixture and stirred at room temperature or at 60 °C.
  • n-BuLi (1.6 M in hexanes, 1.2 mmol, 0.75 ml) was diluted with toluene to a final volume of 3.3 ml and added over 1 h at room temperature using a syringe pump. The reaction was quenched with the addition of 0.1 ml of water. Small aliquots were removed and filtered through silica with ethyl acetate and analyzed by GC/MS and GC/FID.
  • General procedure for the coupling of 4-Chlorotoluene with Acetone A 5 ml screwcap vials with a teflon-coated stir bar and a septum cap was charged in a glovebox with base.
  • the vial was taken outside of the glovebox and Acetone, Arylchloride (1 mmol, 1 eq.) and 0.259 ml tetradecane (1 mmol, 1 eq.) were added via syringe.
  • a second vial was charged with an equimolar amount of the free ligand and palladium source.
  • the catalyst was allowed to preform in 0.5 ml of THF and stirred for 15 minutes.
  • the catalyst solution was added to the reaction mixture and stirred at room temperature for 16h. Small aliquots were removed and filtered through silica with ethyl acetate and analyzed by GC/MS and GC/FID.
  • the catalyst stock solution was added to the vial, fol- lowed by the addition of ammonia in dioxane (0.5 M, 2 ml, 1 mmol) and the mixture was heated to 110 °C in a temperature-controlled aluminum heating block for 5 h. Small aliquots were removed, filtered through silica with ethyl acetate as eluent and were analyzed by GC-FID. Results of Buchwald-Hartwig-Amination Table 1: Results of Buchwald-Hartwig amination reactions:
  • Cond. A 1 mmol ArCl, 1.1 eq. Amine, 1.5 eq. KO t Bu, 0.5 mol% Pd & Ligand, rt, THF; Cond. B: 1 mmol ArCl, 1.1 eq. Amine, 1.5 eq. KO t Bu, 1 mol% Pd & Ligand, rt, THF; Cond. C: 1 mmol ArCl, 1.1 eq. Amine, 1.5 eq. KO t Bu, 0.5 mol% Pd & Ligand, 50 °C, THF.
  • L1-Pd(dba) 32.8 mg (0.058 mmol) of L1 and 39.2 mg (0.058 mmol Pd, 15.6 m% Pd) were suspended in 0.5 ml THF in a J. Young NMR tube. A dark red solution formed that was shaken for 1h. Single crystals of L1-Pd(dba) of pentane into a concentrated solution in THF.
  • L1-Pd(oTol)Br 32.8 mg (0.058 mmol) of L1 and 39.2 mg (0.058 mmol Pd, 15.6 m% Pd) were suspended in 0.5 ml THF in a J. Young NMR tube. A dark red solution formed that was shaken for 1h. Afterwards, 0.1 ml (0.863 mmol, 15 eq.) 4-Bromotoluluene were added and the mixture was shaken overnight. Single crystals of L1-Pd(oTol)Br were obtained by diffusion of Pentane into a con- centrated solution in THF.
  • L2-PdCl2 25.0 mg (0.049 mmol) of L2 and 12.8 mg (0.049 mmol, 1 eq.) Pd(MeCN)2Cl2 were suspended in 0.5 ml THF in a J. 30 Young NMR tube. Quickly a red solution formed that was shaken for 1h during which L2-PdCl2 precipitated as an orange solid.
  • L3-PdCl 2 20.0 mg (0.041 mmol) of L3 and 10.7 mg (0.041 mmol, 1 eq.) Pd(MeCN) 2 Cl 2 were suspended in 0.5 ml THF in a J. Young NMR tube. Quickly a red solution formed that was shaken for 1h dur- ing which L2-PdCl 2 precipitated as an orange solid.
  • L7-PdCl2 25.0 mg (0.043 mmol) of L7 and 11.1 mg (0.043 mmol, 1 eq.) Pd(MeCN)2Cl2 were suspended in 0.5 ml THF in a J. Young NMR tube. Quickly a red solution formed that was shaken for 1h during which L7-PdCl2 precipitated as an orange solid.
  • L1-AuCl 93.3 mg (0.164 mmol) of L1 and 50.0 mg of Au(tht)Cl (0.164 mmol) were suspended in 4 ml Pentane and stirred overnight. A colorless suspension formed and the solid was filtered off, washed with 3x3 ml Pentane and dried in vacuo. L1-AuCl was obtained as a colorless solid in 88 % yield (110 mg, 0.137 mmol).
  • L2-AuCl 83.2 mg (0.164 mmol) of L1 and 50.0 mg of Au(tht)Cl (0.164 mmol) were suspended in 4 ml Pentane and stirred overnight. A colorless suspension formed and the solid was filtered off, washed with 3x3 ml Pentane and dried in vacuo. L2-AuCl was obtained as a colorless solid in 86 % yield (99 mg, 0.134 mmol).
  • L5-AuCl 87.8 mg (0.164 mmol) of L1 and 50.0 mg of Au(tht)Cl (0.164 mmol) were suspended in 4 ml Pentane and stirred overnight. A colorless suspension formed and the solid was filtered off, washed with 3x3 ml Pentane and dried in vacuo. L5-AuCl was obtained as a colorless solid in 54 % yield (65 mg, 0.085 mmol).
  • L6-AuCl 74.6 mg (0.164 mmol) of L1 and 50.0 mg of Au(tht)Cl (0.164 mmol) were suspended in 4 ml Pentane and stirred overnight. A colorless suspension formed and the solid was filtered off, washed with 3x3 ml Pentane and dried in vacuo. L6-AuCl was obtained as a colorless solid in 81 % yield (87 mg, 0.085 mmol).
  • L1-Rh(acac)CO 30.0 mg (0.053 mmol) of L1 and 13.6 mg of Rh(acac)(CO) 2 (0.053 mmol) were suspended in 0.5 ml DCM and for 1 h. Single crystals of L1-Rh(acac)CO were obtained by slow diffusion of Pentane into a concentrated solution in DCM.
  • L2-Rh(acac)CO 25.0 mg (0.049 mmol) of L2 and 12.7 mg of Rh(acac)(CO)2 (0.049 mmol) were suspended in 0.5 ml DCM and for 1 h. Single crystals of L2-Rh(acac)CO were obtained by slow diffusion of Pentane into a concentrated solution in DCM.
  • L3-Rh(acac)CO 25.0 mg (0.051 mmol) of L3 and 13.3 mg of Rh(acac)(CO) 2 (0.051 mmol) were suspended in 0.5 ml DCM and for 1 h. Single crystals of L3-Rh(acac)CO were obtained by slow diffusion of Pentane into a concentrated solution in DCM.

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Abstract

The Invention relates to new ligands of formula 1, wherein R1 is alkyl, perfluoroalkyl, aryl or cycloalkyl, each substituted or unsubstituted, cyano, sulfonyl -SO2-R10 with R10= C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each unsubstituted or substituted with C1-C4 alkyl or C1-C4 perfluoroalkyl; silyl -Si(R20R30R40) with R20, R30 and R40, independently from each other being C1-C6-alkyl or C5-C10 aryl, each unsubstituted or substituted with C1- C4 alkyl; R2 is alkyl, cycloalkyl, adamantyl or aryl, each substituted or unsubstituted; R3, R4 and R5 is alkyl, cycloalkyl or aryl, which each can be unsubstituted or substituted; or at least two of R3, R4 and R5 are an alkyl or alkylether bridge and together with the phosphorus atom, are forming a heterocyclic ring, or wherein R3 and R6 and/or R4 and R7 and/or R5 and R8 are an together forming an alkyl or alkylether bridge, taken together with the nitrogen atom they are connected to, are forming a heterocyclic ring; R6, R7 and R8 are alkyl or aryl, which can be unsubstituted or substituted or, individually or collectively are forming a heterocyclic ring with R3, R4 or R5 and the nitrogen atom they are connected to; m, n and o are 0 or 1, with the proviso that at least one of m, n and o is 1, their metal complexes and use for catalytic purposes.

Description

Mixed P,N-donor ligands, their complexes and use thereof Description Numerous organometallic compounds, especially transition metal and pre- cious metal compounds, are known to be catalysts in chemical synthesis. Nu- merous palladium-catalyzed reactions, such as Heck and Stille reactions, Hartwig-Buchwald reactions, Negishi couplings, Suzuki couplings and So- nogashira couplings are well established in preparative organic chemistry. Nevertheless, there is a constant need for new catalysts that cover specific requirements or have new properties to expand and complement the range of preparative chemistry. WO 2017/093427, for example, shows a palladium-catalyzed selective aryla- tion process. WO 2019/030304 shows the use of novel ligands to prepare metal complexes and their use in organometallic catalysis. A new type of ligands containing nitrogen and phosphorous has been found that surprisingly can form new, previously unknown and catalytically active metal complexes, in particular transition metal compounds. These compounds are ligands of the general formula 1 Formula 1 wherein R1 is alkyl, perfluoroalkyl, aryl or cycloalkyl, each substituted or unsubsti- tuted, cyano, sulfonyl -SO2-R10 with R10= C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each of R1 unsubstituted or substituted with C1-C4 alkyl or C1-C4 perfluoroalkyl; silyl -Si(R20R30R40) with R20, R30 and R40, inde- pendently from each other, being C1-C6-alkyl or C5-C10 aryl, each unsub- stituted or substituted with C1-C4 alkyl; R2 is alkyl, cycloalkyl, adamantyl or aryl, each substituted or unsubstituted; R3, R4 and R5 are alkyl, cycloalkyl or aryl, which each can be unsubstituted or substituted; or at least two of R3, R4 and R5 are an alkyl or alkylether bridge and together with the phosphorus atom, are forming a heterocyclic ring, or wherein R3 and R6 and/or R4 and R7 and/or R5 and R8 are together form- ing an alkyl or alkylether bridge that, taken together with the nitrogen atom they are connected to, are forming a heterocyclic ring; R6, R7 and R8 are alkyl or aryl, which can be unsubstituted or substituted or, individually or collectively are forming a heterocyclic ring with R3, R4 or R5 and the nitrogen atom they are connected to; m, n and o are 0 or 1, with the proviso that at least one of m, n and o is 1. The invention also relates to metal complexes, in particular transition metal and precious metal complexes, comprising at least one ligand of formula 1. The invention also relates to a method for carrying coupling reactions involv- ing such complexes, which might be isolated before use in a coupling reaction or which might be used in a one-pot reaction without isolation of such com- plexes. As is shown in the Examples, the respective ligands of the invention and com- plexes comprising such ligands are effective to enable coupling reactions. The nitrogen substitution leads to significant differences that are not always pre- dictable, but the ligands are behaving very differently from their alkyl/aryl analogs: 1) Structural aspect/stability: The introduction of nitrogen causes the ligands of formula 1 to react mostly as a P,N ligand and not just as a simple mono- phosphane. Some complexes show N-coordination, which is not possible with- out nitrogen. This N-coordination naturally also influences the reactivity, so Pd(0)dba complexes with ligands of formula 1 are significantly more stable. 2) Variation range: Due to the greater range of easy-to-prepare aminophos- phanes from PCl3 and simple amines, it is easier to generate a broader spec- trum of ligands of formula 1 than with alkyl and aryl substituents. This allows easier control of the steric properties and binding ability of the nitrogen. 3) Reactivity: As mentioned, the ligands of formula 1 behave significantly different from their alkyl/aryl analogs. Therefore, in many applications they will probably be less active, as the complexes are more stable. However, there are advantages where additional coordination is required. The best ex- ample to date is the monoarylation of acetone, which only showed very poor selectivities with the YPhos ligands shown in WO 2019/030304. With ligands of formula 1, however, excellent selectivities and yields are possible with one of the catalyst being the best catalyst for this reaction described in literature to date. Short Description of the Invention 1. A ligand of formula 1, Formula 1 wherein R1 is alkyl, perfluoroalkyl, aryl or cycloalkyl, each substituted or unsubstituted, cyano, sulfonyl -SO2-R10 with R10= C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each unsubstituted or substituted with C1-C4 alkyl or C1-C4 perfluoroalkyl; silyl -Si(R20R30R40) with R20, R30 and R40, independently from each other being C1-C6-alkyl or C5-C10 aryl, each unsubstituted or substituted with C1-C4 alkyl; R2 is alkyl, cycloalkyl, adamantyl or aryl, each substituted or unsub- stituted; R3, R4 and R5 is alkyl, cycloalkyl or aryl, which each can be unsubsti- tuted or substituted; or at least two of R3, R4 and R5 are an alkyl or alkylether bridge and together with the phosphorus atom, are forming a heterocyclic ring, or wherein R3 and R6 and/or R4 and R7 and/or R5 and R8 are an to- gether forming an alkyl or alkylether bridge, taken together with the nitrogen atom they are connected to, are forming a heterocyclic ring; R6, R7 and R8 are alkyl or aryl, which can be unsubstituted or substi- tuted or, individually or collectively are forming a heterocyclic ring with R3, R4 or R5 and the nitrogen atom they are connected to; m, n and o are 0 or 1, with the proviso that at least one of m, n and o is 1. A ligand of item 1, wherein R1 is selected from C1 to C9 alkyl, C4-C8 cycloalkyl, C5-C10 aryl, cyano, sulphonyl -SO2-R10 where R10= C1- C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each unsubstituted or substi- tuted by one or more C1 to C4 alkyl, C1 to C4 alkoxy or C1 to C4 per- fluoroalkyl; silyl -Si(R20R30R40) where R20, R30 and R40, each of which is independently C1-C6 alkyl or C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl, or R1 is C5-C10 aryl which may be substituted one or more times by C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl 3. A ligand according to any of the preceding items, wherein R2 is C1 to C9 alkyl, C4-C8 cycloalkyl, adamantyl, C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl. 4. A ligand according to any of the preceding items, wherein R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4-C8 cycloal- kyl, adamantyl, C5 to C10 aryl, which can be unsubstituted or substi- tuted with C1 to C5 alky, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or at least two of R3, R4 and R5 are a C2 to C10 alkyl, C2 to C10 alkenyl or C2 to C10 alkylether bridge and together with the phospho- rus atom, are forming a heterocyclic ring. 5. A ligand according to any of the preceding items, wherein R3, R4 and R5 are, independently from each other, C1 to C5 alkyl, C4-C8 cycloal- kyl, adamantyl, C5 to C6 aryl, which can be unsubstituted or substi- tuted with C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or at least two of R3, R4 and R5 are a C2 to C5 alkyl, C2 to C5 alkenyl or C2 to C4 alkylether bridge and together with the phosphorus atom, are forming a heterocyclic ring. 6. A ligand according to any of the preceding items, wherein at least two of R3, R4 and R5 together are a C2 to C8 alkyl or C2 to C8 alkylether bridge, optionally substituted with one or more C1 to C5 alkyl or cyclo- alkyl groups; or the C2 to C8 alkyl or C2 to C8 alkylether bridge being part of a fused C4 to C8 cycloalkyl ring, forming a heterocyclic ring with the phosphorous atom. 7. A ligand according to any of the preceding items, wherein R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or, individually or collectively are forming a hetero- cyclic ring with R3, R4 or R5 and the nitrogen atom they are connected to. A ligand according to any of the preceding items, wherein R3 and R6 and/or R4 and R7 and/or R5 and R8, taken together are a C2 to C8 al- kyl or C2 to C8 alkylether bridge, optionally substituted with one or more C1 to C5 groups or the C2 to C8 alkyl or C2 to C8 alkylether bridge being part of a fused C4 to C8 cycloalkyl ring, taken together with the nitrogen atom they are connected to, are forming a heterocy- clic ring. A ligand according to any of the preceding items, wherein R1 repre- sents C1 to C9 alkyl, C4-C8 cycloalkyl, C5-C10 aryl, which aryl can be unsubstituted or substituted with C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl. A ligand according to any of the preceding items, wherein R1 is se- lected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert. butyl, n-pentyl, n-pentyl (amyl), 2-pentyl (sec-pentyl), 3-pentyl, 2- methylbutyl, 3-methylbutyl (iso-pentyl or iso-amyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, trifluoro- methyl, cyclobutyl, cyclopentyl, cyclohexyl, menthyl, phenyl, o-toluyl, naphthyl, o-methoxyphenyl, o-ethoxyphenyl, di-(o-methoxy)phenyl, p- trifluoromethylphenyl, trimethylsilyl, triisopropyl-silyl, tri-tert. - bu- tylsilyl, cyano, methylsulfonyl, toluylsulfonyl and trifluoromethyl- sulfonyl. A ligand according to any of the preceding items, wherein R2 is se- lected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert. butyl, n-pentyl, n-pentyl (amyl), 2-pentyl (sec-pentyl), 3-pentyl, 2- methylbutyl, 3-methylbutyl (iso-pentyl or iso-amyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2, 2-dimethylpropyl (neopentyl), n-hexyl, trifluoro- methyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, phenyl, o-, m-, or p-methylphenyl, naphthyl. A ligand according to any of the preceding items, wherein R3, R4, R5, R6, R7 and R8, independently of each other, are selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl butyl, n-pentyl, n-pentyl (amyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methyl- butyl, 3-methylbutyl (iso-pentyl or iso-amyl), 3-methylbut-2-yl, 2- methylbut-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, mesityl. 13. A ligand according to any of the preceding items, wherein at least two or at least one of m, n and o are 1. 14. A ligand according to any of the preceding items, wherein all of m, n and o are 1. 15. A ligand according to any of the preceding items, wherein R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl, sulphonyl -SO2-R10 where R10= C5-C10 aryl, which is unsubstituted or substituted by C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl; R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4- C8 cycloalkyl, adamantyl, C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl; and/or wherein R3 and R6 and/or R4 and R7 and/or R5 and R8, taken together are a C2 to C8 alkyl or C2 to C8 alkylether bridge, optionally said C2 to C8 alkyl bridge may be partially or entirely part of a fused C4 to C8 cyclo- alkyl ring. 16. A ligand according to any of the preceding items, wherein R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl, sulphonyl -SO2-R10 where R10= C5-C10 aryl, which is unsubstituted or substituted by C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl; at least two of of m, n and o are 1; at least two of R3, R4 and R5 together are a C2 to C8 alkyl or C2 to C8 alkylether bridge, optionally substituted with one or more C1 to C5 al- kyl or cycloalkyl groups; or the C2 to C8 alkyl or C2 to C8 alkylether bridge being part of a fused C4 to C8 cycloalkyl ring, forming a hetero- cyclic ring with the phosphorous atom; R6, R7 and/or R8 are C1 to C6 alkyl, or C5-C10 aryl, which is unsubsti- tuted or substituted with one or more C1 to C5 alkyl; with the proviso that if one of R3, R4 and R5 is not a C2 to C8 alkyl bridge or a C2 to C8 alkylether bridge, it is C4-C8 cycloalkyl or ada- mantyl. A ligand according to any of the preceding items, wherein R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl, sulphonyl -SO2-R10 where R10= C5-C10 aryl, which is unsubstituted or substituted by C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl; R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4- C8 cycloalkyl, adamantyl, C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl; and/or wherein R3 and R6 and/or R4 and R7 and/or R5 and R8, taken together are a C2 to C8 alkyl or C2 to C8 alkylether bridge, optionally said C2 to C8 alkyl bridge may be partially or entirely part of a fused C4 to C8 cyclo- alkyl ring. A ligand according to any of the preceding items, wherein R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl; m is 0, n and o are 1 R3 is C4-C8 cycloalkyl or adamantyl; R4 and R5 together are a C2 to C8 alkyl or C2 to C8 alkylether bridge forming a heterocyclic ring with the phosphorous atom, said C2 to C8 alkyl or C2 to C8 alkylether bridge optionally substituted with one or more C1 to C5 alkyl groups; or the C2 to C8 alkyl or C2 to C8 al- kylether bridge entirely or partially being part of a fused C4 to C8 cy- cloalkyl ring; R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubsti- tuted or substituted with one or more C1 to C5 alkyl. 19. A ligand according to any of the preceding items, wherein R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl; m, n and o are 1; and R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4- C8 cycloalkyl or C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl. 20. A ligand according to any of the preceding items, wherein R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl; m, n and o are 1; and R3 and R6, R4 and R7, R5 and R8, each of the pairs taken together are a C2 to C8 alkyl bridge or C2 to C8 alkylether bridge, optionally said C2 to C8 alkyl bridge may be partially or entirely part of a fused C4 to C8 cycloalkyl ring. 21. A ligand according to any of the preceding items, wherein R1 is se- lected from methyl, isopropyl, phenyl, o-tolyl 22. A ligand according to any of the preceding items, wherein R2 is se- lected from methyl, isopropyl, tert.-butyl, cyclohexyl, phenyl and ada- mantyl. 23. A ligand according to any of the preceding items, wherein R3, R4 and R5 is methyl, phenyl, mesityl, 24. A ligand according to any of the preceding items, wherein one or more of R6, R7 and R8 is methyl, isopropyl, isopentyl, neopentyl, phenyl, mesityl. 25. A ligand according to any of the preceding items, wherein R3 and R6 and/or R4 and R7 and/or R5 and R8, taken together with the nitrogen atom they are connected to, are forming a piperidinyl or morpholinyl ring. 26. A ligand according to any of the preceding items, wherein R3 with R6 and R4 with R7 and R5 with R8, taken together with the nitrogen atom they are connected to, are forming a piperidinyl or morpholinyl ring. 27. A metal complex, comprising a transition metal and a ligand of any of items 1 to 26 and optionally comprising at least one organic ligand L and/or at least one halogen X. 28. The metal complex of item 27, the transition metal being a precious metal. 29. The metal complex of item 27 or 28, the transition metal being se- lected from the group consisting of ruthenium, osmium, rhodium, irid- ium, palladium, platinum, silver and gold, in particularly selected from the group consisting of rhodium, iridium, palladium, and gold. 30. The metal complex of any of items 27 to 29, wherein the organic lig- ands are selected from the group consisting of dibenzylidenacetone (DBA), acetylacetone (acac), p-tolyl, m-tolyl, o-tolyl, cyclooctadiene (COD) and carbon monoxide. 31. The metal complex of any of items 27 to 30, wherein the halogen is chlorine or bromine. 32. A method for carrying out a coupling reaction comprising the steps of - providing a reaction mixture comprising at least a substrate, a cou- pling partner and a metal complex comprising a ligand according to any one of items 1 to 26; and - reacting the substrate with the coupling partner in the presence of the metal complex or its derivative to form a coupling product. 33. A method of carrying out a coupling reaction according to claim 32, wherein the metal complex comprising a ligand is a metal complex ac- cording to any one of items 27 to 31. 34. The method of one or more of items 32 or 33, wherein the substrate is a substituted aromatic compound. 35. The method according to item 34, wherein the substituted aromatic compound is an aromatic or heteroaromatic compound. 36. The method according to item 34 or 35, wherein the substituted aro- matic compound is substituted with a leaving group and/or an unsatu- rated aliphatic group or a leaving group. 37. The method according to item 36, wherein the leaving group is se- lected from the group consisting of halogen, triflate, tosylate, nosylate and mesylate, and/or the unsaturated aliphatic group is selected from the group consisting of alkene or alkyne, in particular with 2 to 12, in particular with 2 to 8 carbon atoms. 38. The method according to one or more of the preceding items, wherein the coupling partner is an organometallic compound. 39. The method according to item 38, wherein the organometallic com- pound is selected from the group consisting of organic boron com- pounds, organolithium compounds, organozinc compounds, organolith- ium compounds, organosodium compounds, organopotassium com- pounds and Grignard compounds. 40. The method according to item 38 or 39, wherein the organometallic compound contains at least one aromatic group. 41. The method according to item 38 or 39, wherein the organometallic compound contains at least one unsaturated aliphatic group. 42. The method according to item 38 or 39, wherein the organometallic compound contains at least one saturated aliphatic group. 43. The method according to one or more of items 32 to 42, wherein the coupling reaction can be selected from the group consisting of (i) catalytic hydrofunctionalization reactions of alkynes and alkenes; (ii) catalytic hydroamination reactions of alkynes and alkenes; (iii) catalytic O-H addition reactions on alkynes and alkenes; (iv) catalytic coupling reactions; (v) catalytic Kumada coupling reactions, Murahashi coupling reac- tions, Negishi coupling reactions, or Suzuki coupling reactions, espe- cially for the production of biarylene; (vi) catalytic cross-coupling reactions, in particular C-N and C-O cou- pling reactions; and/or (vii) catalytic Heck coupling reactions, in particular for the prepara- tion of arylated olefins, and Sonogashira coupling reactions, in particu- lar for the preparation of arylated and alkenylated alkynes. (vii) catalytic α-arylations of carbonyl compounds and imines. Detailed Description of the Invention The Invention relates to ligands of formula 1, Formula 1 wherein R1 is alkyl, perfluoroalkyl, aryl or cycloalkyl, each substituted or unsubstituted, cyano, sulfonyl -SO2-R10 with R10= C1-C5 alkyl, C5-C6 cy- cloalkyl, C5-C10 aryl, each unsubstituted or substituted with C1-C4 alkyl or C1-C4 perfluoroalkyl; silyl -Si(R20R30R40) with R20, R30 and R40, inde- pendently from each other being C1-C6-alkyl or C5-C10 aryl, each unsubsti- tuted or substituted with C1-C4 alkyl; R2 is alkyl, cycloalkyl, adamantyl or aryl, each substituted or unsubstituted; R3, R4 and R5 is alkyl, cycloalkyl or aryl, which each can be unsubstituted or substituted; or at least two of R3, R4 and R5 are an alkyl or alkylether bridge and together with the phosphorus atom, are forming a heterocyclic ring, or wherein R3 and R6 and/or R4 and R7 and/or R5 and R8 are an together forming an alkyl or alkylether bridge, taken together with the nitrogen atom they are connected to, are forming a heterocyclic ring; R6, R7 and R8 are alkyl or aryl, which can be unsubstituted or substituted or, individually or collectively are forming a heterocyclic ring with R3, R4 or R5 and the nitrogen atom they are connected to; and m, n and o are 0 or 1, with the proviso that at least one of m, n and o is 1. In general, in the ligands of formula 1 R1 is selected from C1 to C9 alkyl, C4-C8 cycloalkyl, C5-C10 aryl, cyano, sulphonyl -SO2-R10 where R10= C1- C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl, C1 to C4 alkoxy or C1 to C4 perfluoroalkyl; silyl -Si(R20R30R40) where R20, R30 and R40, each of which is inde- pendently C1-C6 alkyl or C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl, or R1 is C5-C10 aryl which may be substituted one or more times by C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl. In a specific embodiment, R1 represents C1 to C9 alkyl, C4-C8 cycloalkyl, C5-C10 aryl, which aryl can be unsubstituted or substituted with C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl. More specifically, R1 is selected from methyl, ethyl, propyl, isopropyl, n-bu- tyl, sec-butyl, tert. butyl, n-pentyl, n-pentyl (amyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (iso-pentyl or iso-amyl), 3-methyl- but-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, trifluo- romethyl, cyclobutyl, cyclopentyl, cyclohexyl, menthyl, phenyl, o-toluyl, naphthyl, o-methoxyphenyl, o-ethoxyphenyl, di-(o-methoxy)phenyl, p-tri- fluoromethylphenyl, trimethylsilyl, triisopropyl-silyl, tri-tert. - butylsilyl, cy- ano, methylsulfonyl, toluylsulfonyl and trifluoromethylsulfonyl. In addition, in the ligands of formula 1 generally is R2 C1 to C9 alkyl, C4-C8 cycloalkyl, adamantyl, C5 to C10 aryl, which can be unsubstituted or substi- tuted with one or more C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 per- fluoroalkyl. More specifically, R2 is selected from methyl, ethyl, propyl, isopropyl, n-bu- tyl, sec-butyl, tert. butyl, n-pentyl, n-pentyl (amyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (iso-pentyl or iso-amyl), 3-methyl- but-2-yl, 2-methylbut-2-yl, 2, 2-dimethylpropyl (neopentyl), n-hexyl, tri- fluoromethyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adaman- tyl, phenyl, o-, m-, or p-methylphenyl, naphthyl. R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4-C8 cycloalkyl, adamantyl, 1-adamantyl, 2-adamantyl, C5 to C10 aryl, which can be unsubstituted or substituted with C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl. In the alternative, at least two of R3, R4 and R5 are a C2 to C10 alkyl, C2 to C10 alkenyl or C2 to C10 alkylether bridge and to- gether with the phosphorus atom, are forming a heterocyclic ring. That means, for example, that while R3 can be a methyl or cyclohexyl ring directly linked to the phosphorous atom when m is 0 (zero), R4 and R5 to- gether could be a C2 alkenyl bridge or a C3 alkyl bridge and with n and o being 1 would form a five-membered unsaturated ring consisting of P, two substituted nitrogen atoms, both linked with the C2 alkenyl bridge or a six- membered saturated ring consisting of P, two substituted nitrogen atoms, both linked with the C3 alkyl bridge. More specifically, R3, R4 and R5 are, independently from each other, C1 to C5 alkyl, C4-C8 cycloalkyl, adamantyl, 1-adamantyl, 2-adamantyl, C5 to C6 aryl, which can be unsubstituted or substituted with C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or at least two of R3, R4 and R5 are a C2 to C5 alkyl, C2 to C5 alkenyl or C2 to C4 alkylether bridge and together with the phosphorus atom, are forming a heterocyclic ring. In another embodiment, at least two of R3, R4 and R5 together are a C2 to C8 alkyl or C2 to C8 alkylether bridge, optionally substituted with one or more C1 to C5 alkyl or cycloalkyl groups; or the C2 to C8 alkyl or C2 to C8 alkylether bridge being part of a fused C4 to C8 cycloalkyl ring, forming a heterocyclic ring with the phosphorous atom. This means, for example, that while R3 can be a methyl or cyclohexyl ring directly linked to the phosphorous atom when m is 0 (zero), R4 and R5 to- gether could be a 1,2-cyclohexyl bridge and with n and o being 1 would form a five-membered unsaturated ring consisting of P, two substituted ni- trogen atoms, each connected to the 1- and 2-position of the cyclohexyl ring providing a C2 alkyl bridge so that the heterocyclic five-membered ring is fused with a cyclohexyl ring. In another embodiment, R6, R7 and R8 are, independently of each other, C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or, R6, R7 and R8 are individually or collectively are forming a heterocyclic ring with R3, R4 or R5 and the nitrogen atom they are connected to. This means that at least one In yet another embodiment, R3 and R6 and/or R4 and R7 and/or R5 and R8, taken together are a C2 to C8 alkyl or C2 to C8 alkylether bridge, op- tionally substituted with one or more C1 to C5 groups or the C2 to C8 alkyl or C2 to C8 alkylether bridge being part of a fused C4 to C8 cycloalkyl ring, taken together with the nitrogen atom they are connected to, are forming a heterocyclic ring. This means that in this embodiment at least one of of m, n and o is 1 and that at least one of R3, R4 or R7 is also linked with the nitrogen atom it is connected to via the respective rest R6, R7 and R8 connected to the same nitrogen atom so as to form an aliphatic ring with the nitrogen atom, op- tionally comprising one or more oxygen atoms as ring members. Specifically, R3 and R6 together may form, for example, an aziridine ring pyrrolidine ring or piperidine ring, or in the case of an alkylether bridge, for example an oxaziridine ring, an oxazolidine ring, an isoxazolidine ring or morpholine ring. The same is possible for R4 with R7, R5 with R8 or for two of or all of R3 with R6, R4 with R7 and R5 with R8. In a further embodiment R3, R4, R5, R6, R7 and R8, independently of each other, are selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl butyl, n-pentyl, n-pentyl (amyl), 2-pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (iso-pentyl or iso-amyl), 3-methyl- but-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, cyclo- butyl, cyclopentyl, cyclohexyl, phenyl, mesityl. In all of the preceding embodiments at least one of m, n and o must be 1. For all ligands in any of the preceding embodiments, it is possible for at least two of m, n and o are 1. In some embodiments if is also possible for a ligand that all of m, n and o are 1. A further embodiment relates to ligands wherein R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl, sulphonyl -SO2-R10 where R10= C5-C10 aryl, which is unsub- stituted or substituted by C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl, which may be 1-ada- mantyl or 2-adamantyl; R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4-C8 cycloalkyl, adamantyl, C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl; and/or wherein R3 and R6 and/or R4 and R7 and/or R5 and R8, taken together are a C2 to C8 alkyl or C2 to C8 alkylether bridge, optionally said C2 to C8 alkyl bridge may be partially or entirely part of a fused C4 to C8 cycloalkyl ring. Yet a further embodiment relates to ligands wherein R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl, sulphonyl -SO2-R10 where R10= C5-C10 aryl, which is unsub- stituted or substituted by C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl, which may be 1-ada- mantyl or 2-adamantyl; at least two of m, n and o are 1; at least two of R3, R4 or R5 together are a C2 to C8 alkyl or C2 to C8 al- kylether bridge, optionally substituted with one or more C1 to C5 alkyl or cycloalkyl groups; or the C2 to C8 alkyl or C2 to C8 alkylether bridge being part of a fused C4 to C8 cycloalkyl ring, forming a heterocyclic ring with the phosphorous atom; R6, R7 and/or R8 are C1 to C6 alkyl, or C5-C10 aryl, which is unsubstituted or substituted with one or more C1 to C5 alkyl; with the proviso that if one of R3, R4 and R5 is not a C2 to C8 alkyl bridge or a C2 to C8 alkylether bridge, it is C4-C8 cycloalkyl or adamantyl, which may be 1-adamantyl or 2-adamantyl. Another embodiment relates to a ligand wherein R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl, sulphonyl -SO2-R10 where R10= C5-C10 aryl, which is unsub- stituted or substituted by C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl, which may be 1-ada- mantyl or 2-adamantyl; R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4-C8 cycloalkyl, adamantyl, which may be 1-adamantyl or 2-adamantyl, C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl; and/or wherein R3 and R6 and/or R4 and R7 and/or R5 and R8, taken together are a C2 to C8 alkyl or C2 to C8 alkylether bridge, optionally said C2 to C8 alkyl bridge may be partially or entirely part of a fused C4 to C8 cycloalkyl ring. Yet another embodiment relates to a ligand wherein R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl, which may be 1-ada- mantyl or 2-adamantyl; m is 0, n and o are 1 R3 is C4-C8 cycloalkyl or adamantyl, which may be 1-adamantyl or 2-ada- mantyl; R4 and R5 together are a C2 to C8 alkyl or C2 to C8 alkylether bridge form- ing a heterocyclic ring with the phosphorous atom, said C2 to C8 alkyl or C2 to C8 alkylether bridge optionally substituted with one or more C1 to C5 al- kyl groups; or the C2 to C8 alkyl or C2 to C8 alkylether bridge entirely or partially being part of a fused C4 to C8 cycloalkyl ring; R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl. A further embodiment relates to ligands wherein R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl, which may be 1-ada- mantyl or 2-adamantyl; m, n and o are 1; and R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4-C8 cycloalkyl or C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl. In another embodiment, a ligand contains the substituents R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl, which may be 1-ada- mantyl or 2-adamantyl; m, n and o are 1; and R3 and R6, R4 and R7, R5 and R8, each of the pairs taken together are a C2 to C8 alkyl bridge or C2 to C8 alkylether bridge, optionally said C2 to C8 al- kyl bridge may be partially or entirely part of a fused C4 to C8 cycloalkyl ring. Specifically, R1 is selected from methyl, isopropyl, phenyl and o-tolyl. Specifically, R2 is selected from methyl, isopropyl, tert.-butyl, cyclohexyl, phenyl and adamantyl, which may be 1-adamantyl or 2-adamantyl. Specifically, R3, R4 and R5 are selected from methyl, phenyl, mesityl. Specifically, one or more of R6, R7 and R8 is methyl, isopropyl, isopentyl, neopentyl, phenyl, mesityl. Specifically, in a ligand according to any of the preceding embodiments, R3 and R6 and/or R4 and R7 and/or R5 and R8, taken together with the nitro- gen atom they are connected to, are forming a piperidinyl or morpholinyl ring. A ligand according to any of the preceding items, wherein R3 with R6 and R4 with R7 and R5 with R8, taken together with the nitrogen atom they are connected to, are forming a piperidinyl or morpholinyl ring and conse- quently, all of m, n and o are equal to 1. The ligands described above are capable of forming metal complexes. Con- sequently, the subject invention also relates to metal complexes comprising a metal, a ligand of formula 1 and optionally comprising at least one organic ligand L and/or at least one halogen X. More specifically, the subject invention also relates to transition metal com- plexes comprising a transition metal and a ligand of formula 1 and option- ally comprising at least one organic ligand L and/or at least one halogen X. Even more specifically, the transition metal is a precious metal. Yet even more specifically, in the transition metal complex of formula 1 the transition metal is selected from the group consisting of ruthenium, os- mium, rhodium, nickel, iridium, palladium, platinum, silver and gold, in par- ticularly selected from the group consisting of rhodium, iridium, palladium and gold. In the transition metal complex of a ligand of formula 1, the organic ligands can be selected from the group consisting of dibenzylidenacetone (DBA), acetylacetone (acac), p-tolyl, m-tolyl, o-tolyl, cyclooctadiene (COD) and carbon monoxide. In the transition metal complex of a ligand of formula 1, the halogen X is chlorine or bromine. The Invention also relates to a method for carrying out a coupling reaction employing a ligand as described above, which preferably is present in a metal complex, in particular a metal complex as described above. More specifically, the invention also relates to a method for carrying out a coupling reaction comprising the steps of - providing a reaction mixture comprising at least a substrate, a cou- pling partner and a metal complex comprising a ligand as described above, particularly the ligand according to any one of items 1 to 26 above; and - reacting the substrate with the coupling partner in the presence of the metal complex or its derivative to form a coupling product. In the method of carrying out a coupling reaction, the metal complex com- prising a ligand is a metal complex as described above, in particular as de- fined in any one of items 27 to 31 above. The substrate can be a substituted unsaturated or substituted aromatic compound, in particular the substituted aromatic compound can be an aro- matic or heteroaromatic compound. The substrate can be substituted, among others, with a leaving group or an unsaturated aliphatic group, whereby it has shown to be useful if the leav- ing group is selected from the group consisting of halogen, in particular Cl, Br or I (chlorine, bromine, iodine), triflate, tosylate, nosylate and mesylate and/or the unsaturated aliphatic group is selected from the group consisting of alkene, or alkyne, in particular with 2 to 12, especially 2 to 8 carbon at- oms. The coupling partner may comprise an organometallic compound, which in particular can be selected from the group consisting of organic boron com- pounds, organic lithium compounds, organic zinc compounds, organic lith- ium compounds and Grignard compounds, wherein advantageously the or- ganometallic compound comprises at least one aromatic group, or wherein the organometallic compound comprises at least one unsaturated aliphatic group, or wherein the organometallic compound comprises at least one sat- urated aliphatic group. Specifically, in the method for carrying out a coupling reaction, the coupling reaction can be selected from the group consisting of (i) catalytic hydrofunctionalization reactions of alkynes and alkenes; (ii) catalytic hydroamination reactions of alkynes and alkenes; (iii) catalytic O-H addition reactions on alkynes and alkenes; (iv) catalytic coupling reactions; (v) catalytic Kumada coupling reactions, Murahashi coupling reactions, Negishi coupling reactions, or Suzuki coupling reactions, especially for the production of biarylene; (vi) catalytic cross-coupling reactions, in particular C-N and C-O coupling reactions; and/or (vii) catalytic Heck coupling reactions, in particular for the preparation of ar- ylated olefins, and Sonogashira coupling reactions, in particular for the preparation of arylated and alkenylated alkynes. (viii) catalytic α-arylations of carbonyl compounds and imines. More specifically, the ligands and their transition metal complexes, in partic- ular their palladium complexes, are particularly useful for the catalytic α-ar- ylations of carbonyl compounds and imines, specifically carbonyl compounds and more specifically ketones. They have been found to be particularly use- ful in the arylation of acetone. For this purpose, ligands of Formula 2 have been found to be particularly useful: Formula 2 wherein A is methyl or o-tolyl, B is cyclohexyl or isopropyl and C is piperidyl or morpholyl, both bound to the P atom via their ring nitrogen atom, such as compounds wherein A, B and C are defined as in the following table: No. A B C 1 Methyl cyclohexyl piperidyl 2 Methyl isopropyl piperidyl 3 Methyl cyclohexyl morpholyl 4 methyl isopropyl morpholyl 5 o-tolyl cyclohexyl piperidyl 6 o-tolyl isopropyl piperidyl 7 o-tolyl cyclohexyl morpholyl 8 o-tolyl isopropyl morpholyl These ligands are used in transition metal complexes as defined above. The invention is explained in more detail in the following examples. These are exemplary for the presentation of the ligands, their preparation and of metal complexes thereof, their preparation and their use in catalysis. The Examples are in no way to be understood as limiting the scope of protection of the invention. Examples Synthesis and Characterization of Amine and Phosphine Precursors: Synthesis of 10-P: N,N'-dimethylethane-1,2-diamine (2.47 g, 3.02 ml, 27.2 mmol) and triethylamine (6.59 g, 9.15 ml, 64.8 mmol) were dissolved in Et2O (150 ml). CyPCl2 (4.80 g, 4.00 ml, 25.9 mmol) was slowly added at -94 °C to obtain a colorless suspension, that was allowed to warm to up to room temperature overnight. The solid was filtered off and was extracted with Et2O (3 x 20 ml). The solvent was removed in vacuo and the oily residue was purified via Kugelrohr distillation (60 °C, 1.0 ∙ 10-3 mbar). The product was obtained as a colorless oil. Yield: (2.85 g, 14.2 mmol, 55%). 3.06 – 2.98 (m, 2H, NCH2), 2.70 – 2.56 (m, 8H, NCH2, NCH3), 1.89 – 1.73 (m, 4H, Cy, H2+3), 1.66 – 1.58 (m, 1H, Cy, H4), 1.44 – 1.35 (m, 1H, Cy, H1), 1.29 – 1.14 (m, 5H, Cy, H2+3+4) ppm. 54.8 (d, 2JCP = 7.0 Hz, NCH2), 41.7 (d, 1JCP = 21.2 Hz, Cy, C1), 40.7 (d, 2JCP = 26.6 Hz, NCH3), 27.6 (d, 3JCP = 17.4 Hz, Cy, C3), 27.1 – 26.9 (m, Cy, C2+4) ppm.31P{1H} NMR (162 MHz, C6D6): δ = 132.4 ppm. IR (ATR): 2918 (s), 2846 (s), 2788 (m), 1445 (m), 1149 (s), 1006 (m), 973 (m), 924 (m), 901 (m), 850 (m), 674 (m), 631 (s), 513 (m), 445 (w) cm-1. Synthesis of 11-P: N,N'-Diisopropylethylenediamine (7.98 g, 10.0 ml, 53,7 mmol) and triethylamine (16.4 g, 22.8 ml, 161 mmol) were dissolved in Et2O (250 ml) and cooled to 0 °C. Phospho- rous trichloride (8.11 g, 5.17 ml, 59.1 mmol) was added drop- wise and the colorless suspension was stirred at room temperature overnight. The solid was filtered off, extracted with Et2O (3 x 50 ml) and all volatiles were removed in vacuo to obtain a yellow oil. The compound was redissolved in Et2O (150 ml) and cooled to 0 °C. CyMgCl (1.35 M in Et2O, 39.8 ml, 53.7 mmol) was added slowly and the suspension was allowed to warm up to room temperature overnight. The solid was filtered off, extracted with Et2O (3 x 50 ml) and the solvent was removed in vacuo. The brown oily residue was extracted with pentane (3 x 30 ml). The solvent was evaporated in vacuo and the residue was purified via Kugelrohr distillation (100 °C, 1.0 ∙ 10-3 mbar). The product was obtained as a colorless oil. Yield: (7.77 g, 30.3 mmol, 57%). 3.20 – 3.00 (m, 4H, CH(CH3)2+ NC2H4N), 2.73 – 2.64 (m, 2H, NC2H4N), 1.96 – 1.86 (m, 2H, Cy, H3ax.), 1.86 – 1.79 (m, 2H, Cy, H2ax.), 1.69 – 1.62 (m, 1H, Cy, H4ax.), 1.43 – 1.32 (m, 1H, Cy, H1), 1.29 – 1.17 (m, 5H, Cy, Heq.), 1.13 (dd, 3JHH = 17.4 Hz, 4JHP = 6.5 Hz, 12H, CH(CH3)2) ppm. NMR (101 MHz, C6D6): δ = 52.4 (d, 2JCP = 23.0 Hz, CH(CH3)2), 50.1 (d, 2JCP = 6.5 Hz, NC2H4N), 41.4 (d, 1JCP = 14.5 Hz, Cy, C1), 28.1 (d, 3JCP = 17.8 Hz, Cy, C3), 27.2 (d, 2JCP = 11.4 Hz, Cy, C2), 27.2 (d, 4JCP = 1.4 Hz, Cy, C4), 23.7 (d, 3JCP = 14.0 Hz, CH(CH3)2), 23.4 (d, 3JCP = 6.5 Hz, CH(CH3)2) ppm. 31P{1H} NMR (162 MHz, C6D6): δ = 107.7 ppm. IR (ATR): 2961 (m), 2918 (s), 2847 (m), 1447 (m), 1379 (m), 1359 (m) 1262 (w), 1166 (s), 1119 (w), 996 (m), 926 (w), 850 (m), 810 (w), 749 (w), 642 (m), 515 (m) cm-1. were . The solution was stirred overnight at room temperature. Sodium borohydride (5.95 g, 150 mmol) was added in small portions and subsequently, the sus- pension was refluxed for 2 h. Water (100 ml) was added and the mixture was extracted with hexane (3 x 200 ml). The organic phase was washed with sat- urated sodium chloride solution (100 ml), dried over magnesium sulfate and the solvent was removed in vacuo. The crude product was obtained as a col- orless oil and was used without further purification. 1H and 13C NMR spectros- copy indicated a purity of approximately 75%. Yield (crude): (4.79 g, 18.0 mmol, 60%). over 2 h, the suspension was filtered and the off-white solid was extracted with Et2O (3 x 50 ml). All volatiles of the combined orange filtrates were re- moved in vacuo. The oily brown residue was purified via Kugelrohr distillation (100 °C, 1.0 ∙ 10-3 mbar). The product was obtained as a colorless oil. Yield: (5.74 g, 21.7 mmol, 28%). NMR (101 MHz, C6D6): δ = 50.1 (d, 2JCP = 10.5 Hz, NCH2CH2), 45.9 (d, 2JCP = 16.0 Hz, NC2H4N), 37.9 (d, 3JCP = 10.1 Hz, NCH2CH2), 26.1 (s, CH), 22.6 (d, 5JCP = 27.4 Hz, CH3) ppm. 31P{1H} NMR (162 MHz, C6D6): δ = 163.0 ppm. IR (ATR): 2954 (s), 2867 (m), 1466 (m), 1366 (m), 1145 (s), 1121 (s), 1061 (s), 699 (m), 413 (s) cm-1. Synthesis of 12-P: 12-Cl (4.58 g, 17.3 mmol) was dissolved Et2O (100 ml) and cooled to 0 °C. CyMgCl (1.35 M in 12.8 ml, 17.3 mmol) was added slowly and the re- suspension was allowed to warm up to room tem- over 2 h. The solid was filtered off, extracted with (3 x 20 ml) and the solvent was removed in vacuo. brown oily residue was stirred in pentane (100 ml). The precipitated solid was filtered off and extracted with pentane (3 x 30 ml). The solvent of the grey filtrate was evaporated in vacuo and the residue was pu- rified via Kugelrohr distillation (120 °C, 1.0 ∙ 10-3 mbar). The product was obtained as a colorless oil. Yield: (3.80 g, 12.1 mmol, 70%). 25.5 Hz, NCH2CH2), 52.7 (d, 2JCP = 6.6 Hz, NC2H4N), 41.5 (d, 1JCP = 16.8 Hz, Cy, C1), 40.6 (d, 3JCP = 9.7 Hz, NCH2CH2),), 27.9 (d, 4JCP = 17.6 Hz, Cy, C3), 27.1 – 27.0 (m, Cy, C2+4), 26.1 (s, CH), 22.9 (d, 5JCP = 19.1 Hz, CH3) ppm. 31P{1H} NMR (162 MHz, C6D6): δ = 128.7 ppm. IR (ATR): 2952 (m), 2919 (s), 2848 (m), 1447 (w), 1366 (w), 1151 (s), 1119 (w) cm-1. Dineopentylethylenediamine (8.23 g, 41.1 mmol) and (12.5 g, 17.4 ml, 123 mmol) were dissolved in (300 ml) and cooled to 0 °C. Phosphorous trichloride g, 3.95 ml, 45.2 mmol) was added dropwise, resulting colorless suspension that turned yellow within 1 h. After suspension was allowed to warm up to room temperature over 2 h, the suspension was filtered and the off-white solid was extracted with Et2O (3 x 50 ml). The solvent of the combined orange filtrates was removed in vacuo. The oily brown residue was purified via Ku- gelrohr sublimation (100 °C, 1.0 ∙ 10-3 mbar). The product was obtained as a colorless crystalline solid. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow evaporation of a saturated benzene solution. Yield: (10.1 g, 38.1 mmol, 93%). (101 MHz, C6D6): δ = 59.9 (d, 2JCP = 14.3 Hz, NC2H4N), 54.2 (d, 2JCP = 10.1 Hz, C), 33.0 (d, 3JCP = 6.6 Hz, C(CH3)3), 28.0 (d, 4JCP = 1.8 Hz, CH3) ppm. 31P{1H} NMR (162 MHz, C6D6): δ = 172.9 ppm. IR (ATR): 2951 (m), 1477 (m), 1392 (w), 1362 (m), 1129 (s), 1077 (m), 1026 (m), 880 (m), 747 (s), 624 (w), 418 (s), 406 (m) cm-1. Melting point: 83 °C. Elemental analysis for C12H26ClN2P: calculated: C 54.43; H 9.90; N 10.58, found: C 54.02; H 10.27; N 10.62. 13-Cl (8.00 g, 30.2 mmol) and triethyla- (5.40 g, 7.50 ml, 53.1 mmol) were dissolved in Et2O ml) and cooled to 0 °C. CyMgCl (1.35 M in Et2O, ml, 53.1 mmol) was added slowly and the resulting was allowed to warm up to room temperature over 2 h. The solid was filtered off, extracted with Et2O (3 x 50 ml) and the solvent was removed in vacuo. The brown oily residue was stirred in pentane (100 ml). The precipitated solid was filtered off and extracted with pentane (3 x 30 ml). The solvent of the grey filtrate was evaporated in vacuo and the residue was purified via Kugelrohr distillation (120 °C, 1.0 ∙ 10-3 mbar). The product crystallizes overnight and was obtained as a colorless solid. Yield: (7.38 g, 23.6 mmol, 78%). 3.18 – 3.11 (m, 2H, NC2H4N), 3.06 (t, 3JHP = 13.7 Hz, 4JHH = 0.9 Hz, 2H, NCH2), 2.69 – 2.58 (m, 2H, NC2H4N), 2.38 (dd, 3JHP = 13.5 Hz, 4JHH = 5.1 Hz, 2H, NCH2), 2.05 – 1.95 (m, 2H, Cy, H3), 1.83 – 1.76 (m, 2H, Cy, H2), 1.66 – 1.59 (m, 1H, Cy, H4), 1.51 – 1.41 (m, 1H, Cy, H1), 1.36 – 1.14 (m, 5H, Cy, H2+3+4), 0.97 (s, 18H, CH3) ppm. NMR (101 MHz, C6D6): δ = 70.7 (d, 2JCP = 26.8 Hz, NCH2), 57.0 (d, 2JCP = 6.7 Hz, NC2H4N), 41.9 (d, 1JCP = 13.3 Hz, Cy, C1), 34.4 (d, 3JCP = 7.6 Hz, C(CH3)3), 28.5 (d, 3JCP = 17.0 Hz, Cy, C3), 28.3 (s, CH3), 27.2 (d, 2JCP = 11.1 Hz, Cy, C2), 26.9 (d, 4JCP = 1.0 Hz, Cy, C4) ppm. 31P{1H} NMR (162 MHz, C6D6): δ = 147.7 ppm. IR (ATR): 2914 (s), 2847 (m), 1474 (w), 1444 (m), 1389 (m), 1360 (s), 1207 (m), 1141 (s), 981 (s), 873 (s), 852 (m), 714 (s), 581 (m), 520 (m), 411 (w), 403 (m) cm-1. Melting point: 35 °C. Elemental analysis for C18H37N2P: calculated: C 69.19; H 11.93; N 8.96, found: C 69.48; H 12.00; N 9.08. Dimesitylethane-1,2-diamine (7.71 g, 26.0 mmol) and (6.61 g, 9.18 ml, 65.0 mmol) were dissolved in (120 ml) and cooled to 0 °C. CyPCl2 (4.82 g, 4.00 ml, mmol) was added dropwise and the mixture was refluxed for 4 d. The solvent of the yellow mixture was removed in vacuo and the residue was extracted with THF (3 x 70 ml). The solvent of the filtrate was removed in vacuo and the residue was washed with Et2O (3 x 5 ml). The crude product was dissolved in hot Et2O (100 ml), was filtered and slowly cooled to -30 °C. Colorless crystals were formed that, were filtered off and were washed with cold Et2O (3 x 10 ml). The product was obtained as color- less crystals in approximately 95% purity according to 31P{1H} NMR spectroscopy and was used without further purification. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by re- crystallisation from hot Et2O. Yield: (3.89 g, 9.52 mmol, 37%). 1H NMR (400 MHz, C6D6): δ = 6.84 (s, 4H, CH, Mesmeta), 3.54 – 3.48 (m, 2H, NCH2), 2.90 – 2.84 (m, 2H, NCH2), 2.72 – 2.27 (m, 12H, CH3, Mesortho), 2.17 (s, 6H, CH3, Mespara), 1.82 – 1.69 (m, 1H, Cy, H1), 1.60 – 1.43 (m, 5H, Cy, H2+H4eq.), 1.25 – 1.11 (m, 2H, Cy, H3eq.), 1.03 – 0.87 (m, 3H, Cy, H3ax.+H4ax.) ppm. 13C{1H} NMR (101 MHz, C6D6): δ = 141.8 (d, 2JCP = 14.4 Hz, Mesipso), 136.1 (s, Mesortho), 134.2 (d, J = 1.7 Hz, Mespara), 130.2 (s, Mesmeta), 52.9 (d, 2JCP = 5.9 Hz, NCH2), 46.7 (d, 1JCP = 37.4 Hz, Cy, C1), 27.4 – 26.4 (m, Cy, C2-4), 21.1 – 19.6 (m, CH3, Mesortho,para) ppm. 31P{1H} NMR (162 MHz, C6D6): δ = 106.1 ppm. -N,N'-Dimethyl-1,2-cyclohexanediamine (2.86 g, mmol) and triethylamine (4.96 g, 6.89 ml, 48.8 mmol) dissolved in Et2O (100 ml) and cooled to 0 °C. At this CyPCl2 was added dropwise to obtain a color- less suspension, that was allowed to warm up to room temperature overnight. The solid was filtered and was extracted with Et2O (3 x 50 ml). The solvent was removed in vacuo. The brown oily residue was purified via Kugelrohr distillation (105 °C, 1.0 ∙ 10-3 mbar). The product was obtained as a colorless oil. Yield: (3.71 g, 14.6 mmol, 75%) 1H NMR (400 MHz, C6D6): δ = 2.76 – 2.69 (m, 1H, Cy(NCH3)2, H1), 2.64 (d, 3JHP = 14.9 Hz, 3H, NCH3), 2.51 (d, 3JHP = 15.0 Hz, 3H, NCH3), 2.13 – 2.05 (m, 1H, Cy(NCH3)2, H1), 1.96 – 1.74 (m, 6H, Cy(NCH3)2+Cy), 1.68 – 1.50 (m, 4H, Cy(NCH3)2+Cy), 1.40 – 0.90 (m, 9H, Cy(NCH3)2+Cy) ppm. 13C{1H} NMR (101 MHz, C6D6): δ = 70.0 (d, 2JCP = 3.6 Hz, Cy(NCH3)2, C1), 67.0 (d, 2JCP = 7.3 Hz, Cy(NCH3)2, C1), 41.1 (d, 1JCP = 27.6 Hz, Cy, C1), 39.2 (d, 2JCP = 33.4 Hz, NCH3), 33.9 (d, 2JCP = 19.0 Hz, NCH3), 31.2 (s, Cy(NCH3)2, C2), 29.1 (d, 3JCP = 2.0 Hz, Cy(NCH3)2, C2), 28.6 (d, 3JCP = 21.3 Hz, Cy, C3), 27.2 – 27.0 (m, Cy, C2+4), 26.9 (d, 3JCP = 11.6 Hz, Cy, C3), 25.0 (s, Cy(NCH3)2, C3), 24.7 (s, Cy(NCH3)2, C3) ppm. 31P{1H} NMR (162 MHz, C6D6): δ = 136.5 ppm. IR (ATR): 2919 (s), 2847 (m), 2787 (w), 1444 (m), 1204 (w), 1149 (m), 1023 (w), 996 (m), 972 (s), 879 (w), 725 (s), 680 (m), 514 (w) cm-1. Synthesis of 16-P: Phosphorous trichloride (2.70 g, 1.75 ml, 20.0 mmol) was dissolved in Et2O (150 ml) and cooled to 0 °C. Slowly, mor- pholine (13.1 g, 13.2 ml, 150 mmol) was added and precip- itation of a white solid started. The suspension was stirred for 1 h at room temperature, the solid was filtered off and was extracted with toluene (3 x 100 ml). All volatiles were removed in vacuo and the product was obtained as a colorless solid. Yield: (5.10 g, 17.6 mmol, 88%). Synthesis of 17-P: N-Methylaniline (17.2 g, 17.5 ml, 160 mmol) and triethylamine (18.6 g, 25.8 ml, 183 mmol) were dissolved in toluene (200 ml) at 0 °C. Phosphorous trichloride (6.28 g, 4.00 ml, 45.7 mmol) was added slowly and the resulting suspension was warmed up to room tem- perature overnight. The solid was filtered off and extracted with hot toluene (3 x 200 ml). The solvent was removed in vacuo to obtain an orange slimy residue, that was washed with Et2O (3 x 50 ml). The product was obtained as an off-white solid. Colorless crystals suitable for single crystal X-ray diffrac- tion experiments were grown by slow evaporation of a saturated benzene solution. Yield: (5.78 g, 16.53 mmol, 36%). Phipso), 129.5 (d, 4JCP = 1.8 Hz, Phmeta), 120.7 (d, 5JCP = 1.3 Hz, Phpara), 117.1 (d, 3JCP = 16.8 Hz, Phortho), 33.4 (d, 2JCP = 5.0 Hz, NCH3) ppm. 31P{1H} NMR (162 MHz, CD2Cl2): δ = 104.4 ppm. IR (ATR): 1591 (m), 1485 (m), 1264 (s), 1177 (m), 1086 (m), 1063 (s), 1025 (m), 988 (w), 832 (s), 748 (s), 693 (m), 677 (s), 605 (m), 425 (s) cm-1. Melting point: 207 °C. Synthesis and Characterization of the Phosphonium Salts: Synthesis of 1·H2: 9 g Tripiperidinylphosphine (31.8 mmol, 1 eq) were dissolved THF and added slowly to a solution of 7.6 ml (63.6 eq.) of benzylbromide in 40 ml THF at 0 °C. It was stirred for 1 h at room temperature and a beige solid precipitated. The sus- pension was filtered and the residue was dissolved in 4 ml DCM and filtered hot. The solution was overlayed with 10 ml pentane. After a day, a white solid precipitated. The solution was filtered off and the solid was washed with 2 x 20 ml pentane. 1·H2 was obtained as a colorless solid (12.1 g, 27.56 mmol, 86 %). 1H-NMR (400 MHz, Chloroform-d): δ = 1.52 – 1.73 (m, 18H, Pip CH2 H2+3), 3.12 (q, 3J = 5.9 Hz, 12H, Pip CH2 H3), 4.39 (d, 2JHP = 15.7 Hz, 2H, PCH2Ph), 7.23 – 7.38 (m, 3H, Phpara + meta CH), 7.43 – 7.51 (m, 2H, Phortho CH). 13C- NMR (101 MHz, Chloroform-d): δ = 23.8 (d, 4JCP = 1.2 Hz, Pip CH2 C3), 25.8 (d, 3JCP = 5.1 Hz, Pip CH2 C2), 30.2 (d, 1JCP = 100.7 Hz, PCH2Ph), 46.9 (s, Pip CH2 C1), 128.1 (d, 2J = 3.6 Hz, Phpara CH), 129.0 (s, Phypso C), 129.0 (d, 4JCP = 3.2 Hz, Phmeta CH), 130.8 (d, 3JCP = 6.1 Hz, Phortho CH). 31P-NMR (162 MHz, Chloroform-d): δ = 50.4 (s). IR (ATR) [cm-1]: 2937 (m), 1453 (w), 1334 (w), 1206 (w), 1157 (m), 1107 (m), 1072 (s), 951 (s), 1024 (w), 795 (m), 705 (m), 527 (w), 493 (m), 462 (w). CHNS: Calculated: C: 58.15, H: 8.21, N: 9.25. Measured: C: 57.95, H: 8.15, N: 9.53. Melting point: 209.9 °C. 4.5 g Tripiperidinylphosphine (15.9 mmol 1 eq.) were dissolved 30 in 80 ml Toluene. 1.53 ml Iodoethane (19.1 mmol, 1.2 eq.) was slowly added and the solution was stirred over night at room temperature. A colorless solid precipitated that was subsequently filtered off, washed with 3 x 10 ml pentane and dried in vacuuo. 2·H2 was obtained as a colorless solid (6.11 g, 13.91 mmol, 88%). 3.07 (q, JHH = 6.1 Hz, 12H, Pip Pos. 1 CH2), 2.61 (dq, J = 13.4, 7.6 Hz, 2H, P–CH2–CH3), 1.68 – 1.46 (m, 18H, Pip Pos. 2 + Pos. 3 CH2), 1.25 – 1.09 (m, 3H, CH3). 13C NMR (101 MHz, CDCl3): δ = 46.3 (d, 2JCP = 1.4 Hz, Pip Pos. 1 CH2), 25.9 (d, 3JCP = 4.8 Hz, Pip Pos. 2 CH2), 23.7 (d, 4JCP = 1.1 Hz, Pip Pos. 3 CH2), 18.0 (d, 1JCP = 105.3 Hz, P–CH2–CH3), 6.6 (d, 3JCP = 5.4 Hz, CH3).31P NMR (162 MHz, CDCl3): δ = 54.5 (s). Synthesis of 3·H2: 3.08 ml cyclohexyldichlorophosphine (20 mmol, 1 eq.) and 7 ml Triethylamine (50 mmol, 2.5 eq.) were dissolved in 30 ml diethylether and cooled to 0 °C. A solution of 2.22 ml N,N-dimetzhylethane-1,2-diamine (20 mmol, 1 eq.) in 50 ml diethylether was prepared and slowly added via an addition funnel at 0 °C over the period of 1h. During the addition a colorless solid precipitated. The mixture was stirred over night at room temperature. The solid was fil- tered off and 3.6 ml benzylbromide (30 mmol, 1.5 eq.) were added to the solution. It was stirred over night during which time a colorless solid precipi- tated that was subsequently filtered off, washed with 3 x 10 ml THF and dried in vacuo. 3·H2 was obtained as a colorless solid (5.4 g, 14.54 mmol, 73%). 3·H2 was used without further purification. Cyclohexyldichlorophosphine (29.2 mmol, 1 eq.) and 12.4 (87.6 mmol, 3 eq.) were dissolved in 50 ml and cooled to 0 °C. A solution of 3.24 ml N,N- dimetzhylethane-1,2-diamine (29.2 mmol, 1 eq.) in 70 ml dieth- ylether was prepared and slowly added via an addition funnel at 0 °C over the period of 1h. During the addition a colorless solid precipitated. The mix- ture was stirred over night at room temperature. The solid was filtered off and 2.34 ml iodoethane (29.2 mmol, 1 eq.) were added to the solution. It was stirred over night during which time a colorless solid precipitated that was subsequently filtered off, washed with 3 x 10 ml THF and dried in vacuo. 4·H2 was obtained as a colorless solid (6.2 g, 17.29 mmol, 60%). 3.39 (d, 3JHP = 7.4 Hz, 4H, MeN(CH2)2NMe), 2.97 – 2.91 (m (overlap), 1H, Cy Pos. 1 CH), 2.89 (d, 3JHP = 9.6 Hz, 6H, NCH3), 2.67 (p, 2JHP = 7.7 Hz, 2H, P-CH2-CH3), 1.93 – 1.70 (m, 5H, Cy Pos. 2+3+4 CH2), 1.49 – 1.18 (m, 5H, Cy Pos. 2+3+4, CH2), 1.10 – 0.98 (m, 3H, P-CH2-CH3). 13C NMR (101 MHz, CD2Cl2): δ = 51.1 (d, 2JCP = 5.0 Hz, MeN(CH2)2NMe), 37.0 (d, 1JCP = 63.3 Hz, Cy Pos. 1 CH), 33.0 (d, 2JCP = 6.2 Hz, NCH3), 25.7 (d, 2JCP = 14.5 Hz, Cy Pos. 2 CH2), 25.5 (d, 4JCP = 1.8 Hz, Cy Pos. 4 CH2), 25.2 (d, 3JCP = 3.6 Hz, Cy Pos. 3 CH2), 16.3 (d, 1JCP = 59.1 Hz, P-CH2-CH3), 4.7 (d, 2JCP = 7.0 Hz, P-CH2-CH3). 31P NMR (162 MHz, CD2Cl2): δ = 84.0 (s). IR (ATR) [cm-1]: 3437 (w), 2925 (m), 2855 (w), 2822 (w), 1480 (w), 1446 (w), 1359 (w), 1251 (w), 1211 (m), 1154 (s), 1044 (vs), 949 (vs), 889 (w), 849 (w), 773 (s), 733 (m), 634 (w), 526 (m), 476 (m), 432 (w). CHNS: Calculated: C: 40.46, H: 7.36, N: 7.86. Measured: C: 40.37, H: 7.56, N: 7.95. Melting point: 191.6 °C (decomposition). Synthesis of 5·H2: g Tripiperidinephosphine (17.6 mmol 1 eq.) were dissolved 80 ml Toluene. 2.44 ml 1-iodo-2-methylpropane (21.1 1.2 eq.) were slowly added, and the solution was stirred overnight under reflux. A beige solid precipitated that was subsequently fil- tered off, washed with 3 x 10 ml pentane and dried in vacuuo. 5·H2 was ob- tained as a crystalline off-white solid (7.35 g, 15.73 mmol, 89%). 3.10 (q, JHH = 5.7 Hz, 12H, Pip Pos. 1 CH2), 2.37 (dd, 2JHP = 13.8, JHH = 6.2 Hz, 2H, P-CH2-iPr), 2.02 (tp, 3JHP = 13.1 Hz, JHH = 6.5 Hz, 1H, iPr CH, 1.66 (m, 6H, Pip Pos. 2 CH2), 1.60 (q (br), JHH = 5.4 Hz, 12H, Pip Pos 3 CH2), 1.14 (d, JHH = 6.7 Hz, 6H, iPr CH3). 13C NMR (101 MHz, CD2Cl2): δ = 46.8 (d, 2JCP = 1.1 Hz, Pip Pos. 1 CH2), 31.7 (d, 1JCP = 100.6 Hz, P-CH2-iPr), 26.0 (d, 2JCP = 5.1 Hz, Pip Pos. 2 CH2), 24.6 (d, 3JCP = 9.8 Hz, iPr CH3), 24.0 (d, 4JCP = 1.2 Hz, Pip Pos. 3 CH2), 23.7 (d, 2JCP = 3.4 Hz, iPr CH). 31P NMR (162 MHz, CD2Cl2): δ = 52.5 (s). IR (ATR) [cm-1]: 3851 (w), 2929 (w), 2848 (w1451 (w), 1377 (w), 1332 (w), 1284 (w), 1201 (w), 1155 (w), 1103 (w), 1073 (s), 1024 (w), 940 (vs), 836 (w), 815 (w), 779 (w), 711 (w), 663 (w), 564 (w), 530 (w), 486 (w), 462 (w). CHNS: Calculated: C: 48.82, H: 8.41, N: 8.99. Measured: C: 48.82, H: 8.49, N: 8.74. Melting point: 195.5 °C. Synthesis of 7·H2: g Tripiperidinephosphine (12.4 mmol 1 eq.) were dis- in 50 ml THF. 2.42 ml 2-methylbenzylchloride (18.6 1.5 eq.) were slowly added, and the solution was for 2 days under reflux. A beige solid precipitated that was subsequently filtered off, washed with 3 x 10 ml pentane and dried in vacuuo. 7·H2 was obtained as off-white solid (3.72 g, 8.77 mmol, 71%). 7.44 – 7.07 (m, 4H, CH oTol), 3.87 (d, 2JHP = 15.7 Hz, 2H, PCH2), 3.05 (q, 3J = 5.8 Hz, 12H, CH2 Pip Pos. 1), 2.45 (d, 4J = 1.4 Hz, 3H, CH3 oTol), 1.69 – 1.62 (m, 6H, CH2 Pip Pos. 3), 1.61 – 1.53 (m, 12H, CH3 Pip Pos. 2). 13C NMR (101 MHz, CD2Cl2): δ = 137.4 (d, 2JCP = 7.7 Hz, C oTol Pos. 1), 131.8 (d, 3JCP = 2.6 Hz, CH oTol Pos. 6), 130.5 (d, J = 5.1 Hz, CH oTol Pos. 4), 128.9 (d, J = 3.5 Hz, CH oTol Pos. 3), 127.8 (d, 3JCP = 7.7 Hz, C oTol Pos. 2), 127.1 (d, J = 3.3 Hz, CH oTol Pos. 5), 47.3 (s, CH2 Pip Pos. 1), 27.6 (d, 1JCP = 108.1 Hz, PCH2), 26.1 (d, 3JCP = 5.1 Hz, CH2, Pip Pos. 2), 24.1 (d, 3JCP = 1.2 Hz, CH2 Pip Pos. 3), 21.1 (s, CH3 oTol). 31P NMR (162 MHz, CD2Cl2): δ = 50.0 (s, Pip3P). IR (ATR) [cm-1]: 2928 (w), 2857 (w), 1494 (w), 1451 (w), 1362 (w), 1336 (w), 1196 (w), 1162 (w), 1099 (w), 1071 (s), 952 (vs), 860 (w), 810 (w), 783 (w), 744 (w), 712 (w), 559 (w), 539 (w), 471 (w), 442 (m). Melting point: 153.8 °C. Synthesis of 10·H2: A solution of 2-methylbenzyl iodide (2.48 g, 10.7 mmol) in THF (30 ml) was added to a solution of 10-P (2.15 g, 10.7 mmol) 30 in THF (30 ml). The resulting colorless suspension was stirred overnight at room temperature. The colorless solid was filtered off and was washed with THF (3 x 20 ml). The phosphonium salt 10·H2 was obtained as a colorless solid. Colorless crystals suitable for single crystal X- ray diffraction experiments were obtained by slow vapor diffusion of Et2O into a saturated acetonitrile solution of the compound. Yield: (4.58 g, 10.6 mmol, 99%). = 5.8 Hz, oTolipso), 131.1 (d, 4JCP = 3.1 Hz, oTolmeta), 130.6 (d, 3JCP = 5.1 Hz, oTolortho), 128.1 (d, 4JCP = 3.5 Hz, oTolmeta’), 126.4 (d, 3JCP = 10.6 Hz, oTolor- tho’), 126.3 (d, 5JCP = 3.3 Hz, oTolpara), 50.6 (d, 2JCP = 4.6 Hz, NC2H4N), 36.8 (d, 1JCP = 59.1 Hz, Cy, C1), 33.5 (d, 2JCP = 6.4 Hz, NCH3), 29.0 (d, 1JCP = 54.6 Hz, CH2oTol), 25.7 – 25.2 (m, Cy, C2-4), 20.7 (d, 4JCP = 1.4 Hz, CH3) ppm. 31P{1H} NMR (162 MHz, CDCl3): δ = 78.2 ppm. IR (ATR): 2851 (w), 1446 (m), 1250 (m), 1223 (m), 1203 (m), 1160 (m), 1144 (m), 1037 (s), 948 (s), 861 (m), 803 (s) 772 (m) 759 (m), 706 (w), 640 (w), 603 (w), 553 (m), 505 (w), 466 (s), 419 (m), 409 (w) cm-1. Melting point: 226 °C. Elemental analysis for C18H30IN2P: calculated: C 50.01; H 6.99; N 6.48, found: C 50.08; H 6.86; N 6.45. Synthesis of 11·H2: A solution of 2-methylbenzyl iodide (6.34 g, 27.3 mmol) in toluene (50 ml) was transferred to a solution of 11-P (7.00 g, 27.3 mmol) in toluene (100 ml). After a few minutes precipi- tation of a colorless solid started and the mixture was stirred at room temperature for 72 h. The colorless solid was filtered off and was washed with toluene (3 x 20 ml) and pentane (3 x 20 ml). The phosphonium salt 11·H2 was obtained as a colorless solid. Colorless crystals suitable single crystal X-ray diffraction experiments were obtained by slow vapor diffusion of pentane into a saturated THF solution of the compound. Yield: (12.7 g, 25.9 mmol, 95%). 7.18 – 7.08 (m, 4H, oTol), 4.06 (d, 1JHP = 10.8 Hz, 2H, CH2oTol), 3.86 – 3.76 (m, 2H, CH(CH3)2), 3.55 – 3.43 (m, 1H, Cy, H1), 3.32 – 3.20 (m, 4H, NC2H4N), 2.41 (s, 3H, C), 2.18 – 2.07 (m, 2H, Cy, H3), 1.90 – 1.74 (m, 3H, Cy, H3+4), 1.70 – 1.55 (m, 2H, Cy, H2), 1.42 – 1.30 (m, 2H, Cy, H2), 1.23 (d, 3JHH = 6.5 Hz, 7H, CH(CH3)2 + Cy, H4), 0.85 (d, 3JHH = 6.5 Hz, 6H, CH(CH3)2) ppm. δ =137.3 (d, 2JCP = 7.6 Hz, oTolipso), 131.5 (d, 4JCP = 2.1 Hz, oTolmeta), 128.6 (d, 3JCP = 5.7 Hz, oTolortho), 128.1 (d, 4JCP = 2.6 Hz, oTolmeta’), 127.6 (d, 3JCP = 9.1 Hz, oTolortho’), 126.5 (d, 5JCP = 2.5 Hz, oTolpara), 45.8 (d, 2JCP = 6.5 Hz, CH(CH3)2), 40.8 (d, 2JCP = 6.4 Hz, NC2H4N), 39.1 (d, 1JCP = 61.6 Hz, Cy, C1), 27.2 (d, 1JCP = 56.9 Hz, CH2oTol), 25.8 (d, 3JCP = 3.6 Hz, Cy, C3), 25.7 – 25.6 (m, Cy, C2), 25.5 (s, Cy, C4) 21.6 (d, 3JCP = 2.7 Hz, CH(CH3)2), 21.2 (s, C), 20.6 (d, 3JCP = 3.3 Hz, CH(CH3)2) ppm. 31P{1H} NMR (162 MHz, CDCl3): δ = 74.5 ppm. IR (ATR): 2932 (w), 1398 (m), 1366 (w), 1197 (m), 1162 (s), 1115 (s), 1057 (m), 880 (w), 790 (w), 766 (w), 747 (m), 737 (m), 546 (m), 522 (w), 509 (m), 470 (s) cm-1. Melting point: 160 °C. Elemental analysis for C22H38IN2P: calculated: C 54.10; H 7.84; N 5.74, found: C 54.35; H 7.78; N 5.67. Synthesis of 12·H2: A solution of 2-methylbenzyl iodide (3.27 g, 14.1 mmol) in Et2O (30 ml) was transferred to a solution of phosphine 12- P in Et2O (100 ml). After a few minutes, precipitation of a colorless solid started and the suspension was stirred at room temperature overnight. The colorless solid was fil- tered off and was washed with Et2O (3 x 50 ml). The crude product was extracted with hot THF (30 ml) and the filtrate was slowly cooled to -30 °C. Colorless crystals formed which were filtered off and washed with cold THF (3 x 5 ml). The phosphonium salt 12·H2 was ob- tained as a colorless solid after drying at 140 °C in vacuo for 10 h. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by recrystallisation from hot toluene. Yield: (3.86 g, 7.08 mmol, 50%). 2JCP = 6.3 Hz, oTolipso), 131.4 (d, 4JCP = 2.8 Hz, oTolmeta), 129.9 (d, 3JCP = 5.1 Hz, oTolortho), 128.2 (d, 4JCP = 3.3 Hz, oTolmeta’), 127.0 (d, 3JCP = 9.9 Hz, oTolor- tho’), 126.5 (d, 5JCP = 3.0 Hz, oTolpara), 47.4 (d, 2JCP = 5.1 Hz, NC2H4N), 44.6 (d, 2JCP = 5.1 Hz, NCH2CH2), 37.6 (d, 1JCP = 60.5 Hz, Cy, C1), 37.4 (d, 3JCP = 4.4 Hz, NCH2CH2), 28.6 (d, 1JCP = 54.0 Hz, CH2oTol), 26.1 (s, CH(CH3)2), 25.7 – 25.4 (m, Cy, C2+3+4), 22.7 (d, 5JCP = 3.6 Hz, CH(CH3)2), 21.2 (s, CH3) ppm. 31P{1H} NMR (162 MHz, CDCl3): δ = 78.1 ppm. IR (ATR): 2925 (m), 2866 (m), 1460 (m), 1366 (w), 1161 (m), 1139 (s), 1069 (s), 864 (m), 800 (m), 757 (m), 554 (m), 540 (m), 508 (m), 465 (s), 416 (m) cm-1. Melt- ing point: 154 °C. Elemental analysis for C26H46IN2P: calculated: C 57.35; H 8.51; N 5.14, found: C 57.40; H 8.56; N 5.11. Synthesis of 13·H2: Phosphine 13-P (6.47 g, 20.7 mmol) and iodoethane (9.69 mg, 4.97 ml, 62.1 mmol) were dissolved in toluene (70 ml). The solution was heated to 70 °C for 5 d. The color- less suspension was filtered and the solid was washed with toluene (3 x 10 ml) and Et2O (3 x 10 ml). The phosphonium salt 13·H2 was obtained as a colorless solid. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained from the combined washing solutions. Yield: (9.24 g, 20.7 mmol, 95%). 2JCP = 4.7 Hz, NC2H4N), 37.2 (d, 1JCP = 62.3 Hz, Cy, C1), 33.8 (d, 3JCP = 5.3 Hz, C(CH3)3), 28.5 (s, C(CH3)3), 25.5 (d, 3JCP = 14.3 Hz, Cy, C3), 25.3 (d, 4JCP = 1.8 Hz, Cy, C4), 24.9 (d, 2JCP = 3.6 Hz, Cy, C2), 17.9 (d, 1JCP = 58.2 Hz, CH2CH3), 4.7 (d, 2JCP = 7.4 Hz, CH2CH3) ppm. 31P{1H} NMR (162 MHz, CDCl3): δ = 91.3 ppm. IR (ATR): 2940 (w), 1363 (w), 1128 (s), 1095 (m), 1032 (m), 887 (m), 849 (w), 791 (m), 736 (m), 564 (m), 471 (m) cm-1. Melting point: 217 °C. Elemental analysis for C20H42IN2P: calculated: C 51.28; H 9.04; N 5.98, found: C 51.31; H 9.31; N 5.98. Synthesis of 14·H2: Phosphine 14-P (528 mg, 1.29 mmol) and iodoethane (2.01 g, 1.03 ml, 12.9 mmol) were dissolved in toluene (20 ml) and the mixture was heated to 60 °C overnight. All volatiles were re- moved in vacuo. The oily residue was suspended in Et2O (20 ml), was frozen and a colorless suspension was obtained when the mix- ture was allowed to warm up to room temperature. The colorless solid was filtered off and was washed with Et2O (3 x 10 ml). The crude phosphonium salt 14·H2 was obtained as a colorless solid in 90% purity according to 31P{1H} NMR spectroscopy. Yield: (300 mg, 0.478 mmol, 37%). 1H NMR (400 MHz, CDCl3): δ = 6.94 (s, 4H, Mesmeta), 4.05 – 3.86 (m, 4H, NCH2), 2.65 – 2.52 (m, 2H, CH2CH3), 2.47 (s, 6H, Mespara, CH3), 2.44 (s, 6H, Mesortho, CH3), 2.37 – 2.29 (m, 1H, Cy, H1), 2.27 (s, 6H, Mesortho’, CH3), 1.77 – 1.66 (m, 3H, Cy, H3+4), 1.59 – 1.50 (m, 2H, Cy, H2), 1.33 – 1.13 (m, 8H, Cy, H2+3+4, CH2CH3) ppm. 13C{1H} NMR (101 MHz, CDCl3): δ = 139.3 (d, 5JCP = 1.4 Hz, Mespara), 137.5 (d, 3JCP = 1.8 Hz, Mesortho), 137.4 (d, 3JCP = 2f.1 Hz, Mesortho’), 132.7 (d, 2JCP = 4.9 Hz, Mesipso), 131.0 (s, Mesmeta), 130.6 (s, Mesmeta’), 52.1 (d, 2JCP = 8.4 Hz, NCH2), 41.9 (d, 1JCP = 60.0 Hz, Cy, C1), 26.5 (d, 3JCP = 14.0 Hz, Cy, C3), 26.2 (d, 2JCP = 2.9 Hz, Cy, C2), 25.5 (d, 4JCP = 1.8 Hz, Cy, C4), 21.7 (d, 1JCP = 61.2 Hz, CH2CH3), 21.0 (s, Mespara, CH3), 20.1(s, Mesortho, CH3), 19.4 (s, Mesortho’, CH3), 7.6 (d, 2JCP = 4.7 Hz, CH2CH3) ppm. 31P{1H} NMR (162 MHz, CDCl3): δ = 66.8 ppm. solution of 2-methylbenzyl iodide (3.04 g, 13.1 mmol) in HF (30 ml) was added to a solution of the phosphine 15- (3.34 g, 13.1 mmol) in THF (30 ml). The resulting white suspension was stirred overnight at room temperature. The colorless solid was filtered off and was washed with THF (3 x 20 ml). The phosphonium salt 15·H2was obtained as a colorless solid. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow vapor diffusion of Et2O into a saturated chloroform solution of the compound. Yield: (6.33 g, 13.0 mmol, 99%). 1H NMR (400 MHz, CDCl3): δ = 7.36 – 7.31 (m, 1H, oTolortho), 7.21 – 7.10 (m, 3H, oTolmeta+para), 4.39 – 4.21 (m, 2H, Cy(NCH3)2, H1), 3.68 – 3.58 (m, 1H, Cy, H1), 2.92 (d, 3JHP = 10.9 Hz, 3H, NCH3), 2.85 (d, 3JHP = 11.2 Hz, 3H, NCH3), 2.66 – 2.57 (m, 1H, Cy(NCH3)2, H1), 2.39 (s, 3H, CH3), 2.29 – 2.19 (m, 1H, Cy, H3), 2.12 – 2.02 (m, 1H, Cy(NCH3)2, H2), 2.01 – 1.75 (m, 9H, Cy(NCH3)2, H3+4, Cy, H2+3+4), 1.67 – 1.54 (m, 2H, Cy, H2+3+4), 1.51 – 1.34 (m, 2H, Cy, H2+3+4), 1.31 – 1.15 (m, 2H, Cy(NCH3)2, H4), 1.12 – 1.00 (m, 2H, Cy(NCH3)2, H3+4), 0.96 – 0.82 (m, 1H, Cy(NCH3)2, H3) ppm. 13C{1H} NMR (101 MHz, CDCl3): δ = 137.6 (d, 2JCP = 5.5 Hz, oTolipso), 131.3 (d, 3JCP = 4.9 Hz, oTolortho), 131.0 (d, 4JCP = 3.2 Hz, oTolmeta), 128.2 (d, 4JCP = 3.6 Hz, oTolmeta), 126.4 (d, 3JCP = 10.5 Hz, oTolortho’), 126.1 (d, 5JCP = 3.3 Hz, oTolpara), 66.5 (d, 2JCP = 3.0 Hz, Cy(NCH3)2, C1), 65.7 (d, 2JCP = 2.7 Hz, Cy(NCH3)2, C1), 36.5 (d, 1JCP = 57.2 Hz, Cy, C1), 30.4 (d, 2JCP = 4.3 Hz, NCH3), 30.2 (d, 2JCP = 5.0 Hz, NCH3), 28.8 (d, 1JCP = 52.9 Hz, CH2oTol), 27.77 (d, 3JCP = 1.8 Hz, Cy(NCH3)2, C2), 27.71 (d, 3JCP = 1.4 Hz, Cy(NCH3)2, C2’), 25.9 (d, 3JCP = 4.0 Hz, Cy, C3), 25.7 (d, 3JCP = 14.2 Hz, Cy, C3), 25.5 – 25.3 (m, Cy, C2+4), 23.6 (d, 4JCP = 1.8 Hz, Cy(NCH3)2, C3), 20.8 (d, 4JCP = 1.4 Hz, CH3) ppm. 31P{1H} NMR (162 MHz, CDCl3): δ = 78.7 ppm. IR (ATR): 2921 (w), 2854 (w), 1444 (m), 1246 (w), 1198 (m), 1170 (m), 1152 (w), 1120 (w), 1016 (s), 921 (w), 901 (m), 857 (w), 834 (w), 811 (w), 788 (w), 751 (m), 729 (w), 555 (m), 478 (m), 463 (m) cm-1. Melting point: 273 °C. Elemental analysis for C22H36IN2P: calculated: C 54.32; H 7.46; N 5.76, found: C 54.22; H 7.32; N 5.61. Synthesis of 16·H2: Trimorpholinophosphine 16-P (3.00 g, 10.4 mmol) and 2- methylbenzyl iodide (2.41 g, 10.4 mmol) were dissolved in THF (70 ml) and stirred overnight. A colorless suspension was formed and was filtered. The off-white solid was washed with THF (3 x 20 ml) and DCM (3 x 10 ml). The phosphonium salt 16·H2 was obtained as a color- less solid after drying for 10 h at 100 °C in vacuo. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow vapor diffusion of Et2O into a saturated acetonitrile solution of the compound. Yield: (4.54 g, 8.70 mmol, 84%). CD3CN): δ = 138.6 (d, 2JCP = 8.6 Hz, oTolipso), 132.4 (d, 4JCP = 2.2 Hz, oTolmeta), 131.0 (d, 3JCP = 5.1 Hz, oTolortho), 129.5 (d, 4JCP = 3.2 Hz, oTolmeta’), 128.1 (d, 3JCP = 7.4 Hz, oTolortho’), 127.8 (d, 5JCP = 3.0 Hz, oTolpara), 66.9 (d, 2JCP = 5.3 Hz, Mor, C2), 46.5 (Mor, C3), 26.3 (d, 1JCP = 105.7 Hz, CH2oTol), 20.9 (CH3) ppm.31P{1H} NMR (162 MHz, CD3CN): δ = 49.3 ppm. IR (ATR): 1353 (w), 1252 (w), 1131 (m), 1107 (s), 957 (s), 923 (m), 845 (w), 794 (m), 748 (w), 716 (w), 509 (w), 460 (m) cm-1. Melting point: 252 °C. Ele- mental analysis for C20H33IN3O3P: calculated: C 46.07; H 6.38; N 8.06, found: C 45.92; H 8.08; N 6.37. 25 Tris(N-methylaniline)phosphine 17-P (4.00 g, 11.4 mmol) I and iodoethane (5.33 g, 2.74 ml, 34.2 mmol) were sus- (PhNMe)3P pended in toluene (25 ml) and mixture was heated to 90 °C for 9 d. A brown solid was formed, that was separated from the brown solu- tion. Acetonitrile (30 ml) was added and the resulting brown solution was treated with Et2O (100 ml). Crude 17·H2 was obtained as a brown solid after filtration and was used without further purification. Iminobibenzyl (1.95 g, 10 mmol) was dissolved in THF (25 ml) and was treated slowly with n-BuLi (1.6 M, 4.25 ml, 10 mmol) at -90 °C. The resulting colorless suspension was stirred at -90 °C for 1 h and iPr2PCl (1.53 ml, 10 mmol) was added subsequently and the reaction mixture was warmed up to room temperature. Benzyl bromide was added and the resulting color- less suspension was stirred overnight. The colorless solid was filtered off and was washed with THF (3 x 10 ml). The product was used without further pu- rification for the next step. Synthesis and Characterization of the Ligands: Synthesis of L1: 5 g (11 mmol, 1 eq.) Phosphonium salt 1·H2 was suspended in 15 50 ml THF and deprotonated by slow addition of 6.9 ml of a n- BuLi solution (1.6 M in hexane, 11 mmol, 1 eq.) until a clear, slightly yellow solution was formed. The solution was stirred for 45 min and then 2.42 ml (11 mmol, 1 eq) of the respective chlorophosphine were added at room temperature. A colorless solid precipi- tated shortly after addition. The suspension was stirred for 2 h and then 6.9 ml of a n-BuLi solution (1.6 M in hexane, 11 mmol, 1 eq.) were slowly added until a clear, yellow solution was formed. The solution was stirred for 30 min and the solvent was subsequently removed in vacuuo. The residue was sus- pended in 50 ml acetonitrile and stirred overnight, forming a colorless solid. The solid was filtered off, washed with acetonitrile 2 x 20 ml and dried in vacuo thus giving L1 (4.87 g, 8.55 mmol, 78%) as a colorless solid. 1H-NMR (400 MHz, CD2Cl2): δ = 0.96 – 1.36 (m, 10H, PCy2 CH2 H2+3+4), 1.49 (q, 12H, 3J = 5.4 Hz, Pip CH2 H2), 1.53 – 1.59 (m, 6H, Pip CH2 H3), 1.59 – 1.68 (m, 6H, PCy2 CH2 H2+3+4), 1.69 – 1.77 (m, 2H, PCy2 CH2 H2+3+4), 1.80 – 1.89 (m, 3H, PCy2 CH2 H2+3+4), 2.18 (tdt, 2JHP = 10.6 Hz, 4JHP = 6.4 Hz, 3J = 3.2 Hz, 2H, PCy2 CH H1), 3.07 (q, 3JHP = 5.4 Hz, 6H, Pip CH2 H1), 6.47 (m, 1H, Phpara), 6.88 (m, 2H, Phortho), 6.98 (m, 2H, Phmeta). 13C-NMR (101 MHz, Methylene Chloride-d2): δ = 25.4 (s, Pip CH2 C3), 26.9 (d, 3JCP = 4.7 Hz, Pip CH2 C2), 27.2 (d, 2J = 1.4 Hz, PCy2 CH2 C2+3+4), 27.8 – 28.4 (m, PCy2 CH2 C2+3+4), 31.7 (m, PCy2 CH2 C2+3+4), 34.9 (m, PCy2 CH2 C2+3+4), 36.0 (dd, 1JCP = 14.4 Hz, 3JCP = 8.5 Hz, PCy2 CH C1), 38.4 (dd, 1JCP = 173.8 Hz, 29.0 Hz), 48.4 (dd, 2JCP = 5.8 Hz, 3JCP = 1.4 Hz, Pip CH2 C1), 115.7 (s, Phpara), 124.0 (d, 2JCP = 12.5 Hz, Phortho), 127.4 (d, 4JCP = 1.5 Hz, Phmeta), 148.1 (d, 2JCP = 13.2 Hz, Phypso). 31P-NMR (162 MHz, Methylene Chloride-d2): δ = -7.63 (d, 2JPP = 195.2 Hz, PCy2), 56.2 (d, 2JPP = 195.5 Hz, P(Pip)3). IR (ATR) [cm-1]: 2915 (m), 2841 (w), 1589 (w), 1485 (w), 1232 (m), 1155 (m), 1116 (w), 1059 (s), 1024 (m), 983 (m), 917 (m), 851 (w), 745 (s), 701 (m), 642 (w), 540 (m), 472 (m), 416 (w). Melting point: 216.6 °C. HRMS (ESI): m/z C34H58N3P2 [M+H]+ Calculated: 570.4101 Found: 570.4092. Synthesis of L2: 2.7 g (6.15 mmol, 1 eq.) Phosphonium salt 2·H2 was suspended 15 in 40 ml THF and deprotonated by slow addition of 4 ml of a n- BuLi solution (1.55 M in hexane, 6.15 mmol, 1 eq.) until a clear solution was formed. The solution was stirred for 45 min and then 1.36 ml of dicyclohexylchlorophosphine (6.15 mmol, 1 eq.) were added at room tem- perature. A colorless solid precipitated shortly after addition. The suspension was stirred for 2 h and then 4 ml of a n-BuLi solution (1.55 M in hexane, 6.15 mmol, 1 eq.) were slowly added until a clear, yellow solution was formed. The solution was stirred for 30 min and the solvent was subsequently removed in vacuuo. The residue was suspended in 30 ml acetonitrile and stirred overnight, forming a colorless solid. The solid was filtered off, washed with acetonitrile 2 x 10 ml and dried in vacuo thus giving L2 (2.71 g, 5.34 mmol, 89%) as a colorless solid. 3.08 (q, 3J = 5.2 Hz, 12H, Pip Pos.1, CH2), 1.86 (d, 3J = 11.7 Hz, 2H, Cy Pos.3, CH2), 1.78 – 1.63 (m, 10H, Cy Pos.1, CH + Cy Pos.2 + Pos.3, CH2), 1.61 – 1.42 (m, 21H, CH3 + Pip Pos.2 + Pos.3, CH2), 1.33 – 1.11 (m, 10H, Cy Pos.3 + Pos.2, CH2). 13C NMR (101 MHz, THF): δ = 48.6 (d, 2JCP = 5.1 Hz, Pip Pos. 1, CH2), 35.6 (dd, 1JCP = 13.8 Hz, 3JCP = 8.8 Hz, Cy Pos.1, CH), 33.3 (d, 2JCP = 19.9 Hz, Cy Pos.2, CH2), 32.2 (d, 3JCP = 9.2 Hz, Cy Pos.3, CH2), 29.1 (d, 3JCP = 6.9 Hz, Cy Pos.3, CH2), 28.9 (d, 2JCP = 12.4 Hz, Cy Pos.2, CH2), 28.3 (s, Cy Pos.4, CH2), 27.9 (d, 3JCP = 5.2 Hz, Pip Pos.2, CH2), 26.3 (s, Pip Pos.3, CH2), 15.4 (d, 2JCP = 9.7 Hz, CH3), 13.5 (dd, 1JCP = 195.5, 19.8 Hz, P–C-–P). 31P NMR (162 MHz, THF): δ = 60.9 (d, 2JPP = 191.8 Hz, P+Pip3), -4.3 (d, 2JPP = 192.0 Hz, PCy2). IR (ATR) [cm-1]: 3388 (w), 2917 (m), 2845 (w), 2821 (w), 1632 (w), 1442 (w), 1364 (w), 1325 (w), 1213 (w), 1153 (w), 1120 (w), 1048 (m), 1024 (w), 935 (vs), 894 (m), 846 (w), 719 (w), 692 (m), 670 (w), 612 (w), 556 (w), 509 (w), 470 (w), 427 (w). Melting point: 110.6 °C. HRMS (ESI): m/z C29H56N3P2 [M+H]+ Calculated: 508.3944 Found: 508.3936. Synthesis of L3: 4.5 g (12.1 mmol, 1 eq.) Phosphonium salt 3·H2 was sus- pended in 50 ml THF and deprotonated by slow addition of 7.8 ml of a n-BuLi solution (1.55 M in hexane, 12.1 mmol, 1 eq.) until a clear, slightly yellow solution was formed. The solution was stirred for 45 min and then 2.67 ml of dicyclohexylchlorophosphine (12.1 mmol, 1 eq.) were added at room temperature. A colorless solid precipitated shortly after addition. The suspension was stirred for 2 h and then 7.8 ml of a n-BuLi solution (1.55 M in hexane, 12.1 mmol, 1 eq.) were slowly added until a clear, yellow solution was formed. The solution was stirred for 30 min and the sol- vent was subsequently removed in vacuuo. The residue was suspended in 50 ml acetonitrile and stirred overnight, forming a colorless solid. The solid was filtered off, washed with acetonitrile 2 x 20 ml and dried in vacuo thus giving L3 (4.26 g, 8.76 mmol, 72%) as a colorless solid. 7.33 – 7.27 (m, 4H, Phortho + Phmeta CH), 7.04 – 6.97 (m, 1H, Phpara CH), 3.27 (br, 1H, P+Cy Pos. 1 CH), 2.78 – 2.54 (m, 4H, MeN(CH2)2NMe), 2.45 (d, JHH = 8.9 Hz, 6H, NCH3), 2.33 – 2.22 (m, 2H, PCy2 Pos. 2 CH2), 2.17 – 1.96 (m, 6H, PCy2 Pos. 1 CH + Pos. 3 CH2), 1.88 – 1.78 (m, 4H, P+Cy Pos. 3 CH2), 1.77 – 1.65 (m, 4H, PCy2 Pos. 2 CH2), 1.65 – 1.50 (m, 4H, P+Cy Pos. 2 + Pos. 4 CH2), 1.46 – 1.10 (m, 12H, P+Cy Pos. 2 + PCy2 Pos. 2 + Pos. 3 + Pos. 4 CH2).13C NMR (101 MHz, C6D6): δ = 144.8 (dd, 2JCP = 5.6, 3.3 Hz, Phypso C), 129.6 (s, Phmeta), 127.5 (s, Phortho), 121.7 (s, Phpara), 48.0 (d, 2JCP = 5.1 Hz, MeN(CH2)2NMe), 37.8 (dd, 1JCP = 90.8 Hz, 3JCP = 18.0 Hz, P+Cy Pos. 1 CH), 36.9 (dd, 1JCP = 13.5 Hz, 3JCP = 8.1 Hz, PCy2 Pos. 1 CH2), 34.3 (dd, 1JCP = 131.3, 30.5 Hz, P–C-–P), 33.1 (d, 2JCP = 6.3 Hz, NCH3), 32.7 (d, 2JCP = 20.2 Hz, P+Cy Pos. 2 CH2), 30.9 (d, 3JCP = 8.8 Hz, PCy2 Pos. 3 CH2), 28.0 (d, 3JCP = 7.7 Hz, PCy2 Pos. 3 CH2), 27.7 (d, 3JCP = 12.5 Hz, P+Cy Pos. 3 CH2), 27.1 (s, PCy2 Pos. 4 CH2), 26.5 (d, 2JCP = 14.0 Hz, PCy2 Pos. 2 CH2), 26.2 (s, P+Cy Pos. 4 CH2). 31P NMR (162 MHz, C6D6): δ = 62.9 (d, 2JPP = 177.5 Hz, P+Cy), -5.4 (d, 2JPP = 178.0 Hz PCy2). IR (ATR) [cm-1]: 3386 (w), 3069 (w), 2920 (m), 2843 (w), 1632 (w), 1587 (w), 1483 (w), 1443 (w), 1345 (w), 1226 (m), 1173 (w), 1116 (w), 1038 (s), 1000 (w), 945 (w), 915 (m), 850 (w), 758 (w), 703 (vs), 675 (m), 637 (m), 537 (vs), 500 (vs), 427 (m), 404 (m). Melting point: 155.2 °C. HRMS (ESI): m/z C29H49N2P2 [M+H]+ Calculated: 487.3433 Found: 487.3358 Synthesis of L4: 15 2.6 g (7.3 mmol, 1 eq.) Phosphonium salt 4·H2 was suspended in ml THF and deprotonated by slow addition of 4.7 ml of a n-BuLi solution (1.55 M in hexane, 7.3 mmol, 1 eq.) until a clear, slightly yellow solution was formed. The solution was stirred for 45 min and then 1.61 ml of dicyclohexylchlorophosphine (7.3 mmol, 1 eq.) were added at room temperature. A colorless solid precipitated shortly after addi- tion. The suspension was stirred for 2 h and then 4.7 ml of a n-BuLi solution (1.55 M in hexane, 7.3 mmol, 1 eq.) were slowly added until a clear, yellow solution was formed. The solution was stirred for 30 min and the solvent was subsequently removed in vacuuo. The residue was suspended in 30 ml ace- tonitrile and stirred overnight, forming a colorless solid. The solid was filtered off, washed with acetonitrile 2 x 10 ml and dried in vacuo thus giving L4 (2.22 g, 5.22 mmol, 72%) as a colorless solid. 3.06 (s, 1H, P+Cy Pos. 1 CH), 2.83 – 2.61 (m, 4H, MeN(CH2)2NMe), 2.52 (d, 3JHP = 9.1 Hz, 6H, NCH3), 2.27 – 2.16 (m, 2H, PCy2 Pos. 3 CH2), 2.13 – 2.03 (m, 4H, P+Cy Pos. 2 + PCy2 Pos. 2 CH2), 2.02 – 1.85 (m, 6H, PCy2 Pos. 1 CH + PCy2 Pos. 2 + Pos. 3 CH2), 1.80 – 1.74 (m, 2H, PCy2 Pos. 4 CH2), 1.74 – 1.66 (m, 2H, P+Cy Pos. 3 CH2), 1.65 – 1.06 (m, 24H, P+Cy Pos. 2 + Pos. 3 + Pos. 4 CH2 + PCy2 Pos. 2 + Pos. 3 + Pos. 4 CH2). 13C NMR (101 MHz, C6D6): δ = 48.5 (d, 2JCP = 4.8 Hz, MeN(CH2)2NMe), 36.7 (dd, 1JCP = 88.0 Hz, 3JCP = 14.3 Hz, P+Cy Pos. 1 CH), 35.6 (dd, 1JCP = 12.5 Hz, 3JCP = 8.3 Hz CH), 33.6 (d, 2JCP = 6.1 Hz, NMe), 32.9 (d, 2JCP = 20.5 Hz, PCy2 Pos. 2 CH2), 31.6 (d, 3JCP = 7.4 Hz, PCy2 Pos. 3 CH2), 28.7 (dd, 2JCP = 6.3, 4JCP = 4.6 Hz, P+Cy Pos. 2 CH2), 28.5 (d, 3JCP = 6.6 Hz, PCy2 Pos. 3 CH2), 28.3 (d, 2JCP = 12.8 Hz, PCy2 Pos. 2 CH2), 27.6 (s, PCy2 Pos. 4 CH2), 26.8 (d, 3JCP = 13.7 Hz, PCy2 Pos. 3 CH2), 26.6 (d, 4JCP = 1.8 Hz, P+Cy Pos. 4 CH2), 17.0 (dd, 1JCP = 140.4, 21.8 Hz, P–C-–P), 11.8 (dd, 2JCP = 4.8, 2.4 Hz, P–C— CH3). 31P NMR (162 MHz, C6D6): δ = 68.6 (d, 2JPP = 172.0 Hz, P+Cy), -2.9 (d, 2JPP = 171.4 Hz, PCy2). IR (ATR) [cm-1]: 3389 (w), 2917 (m), 2844 (s), 1633 (w), 1444 (w), 1346 (w), 1234 (w), 1206 (w), 1165 (s), 1093 (w), 1035 (s), 942 (s), 922 (s), 887 (m), 852 (w), 761 (w), 667 (m), 607 (s), 511 (m), 476 (s), 411 (vs). Melting point: 122.0 °C. HRMS (ESI): m/z C24H47N2P2 [M+H]+ Calculated: 425.3209 Found: 425.3204. (2.14 mmol, 1 eq.) Phosphonium salt 5·H2 was suspended ml THF and deprotonated by slow addition of 1.38 ml of a n-BuLi solution (1.55 M in hexane, 2.14 mmol, 1 eq.) until a clear, slightly yellow solution was formed. The solution was stirred for 45 min and then 0.47 ml of dicyclohexylchlorophosphine (2.14 mmol, 1 eq.) were added at room temperature. A colorless solid precipitated shortly after addi- tion. The suspension was stirred for 2 h and then 1.38 ml of a n-BuLi solution (1.55 M in hexane, 2.14 mmol, 1 eq.) were slowly added until a clear, yellow solution was formed. The solution was stirred for 30 min and the solvent was subsequently removed in vacuuo. The residue was suspended in 30 ml ace- tonitrile and stirred overnight, forming a colorless solid. The solid was filtered off, washed with acetonitrile 2 x 15 ml and dried in vacuo thus giving L5 (1 g, 2.14 mmol, 87%) as a colorless solid. 1H NMR (400 MHz, C6D6): δ = 3.10 (q, JHH = 5.1 Hz, 12H, Pip Pos. 1 CH2), 2.76 (tdd, 3JHP = 13.8, 11.2 Hz, JHH = 6.9 Hz, 1H, iPr CH3), 2.42 – 2.29 (m, 2H, Cy Pos. 2 CH2), 2.23 – 2.09 (m, 4H, Cy Pos. 2 CH2 + Pos. 1 CH), 2.02 – 1.87 (m, 4H, Cy Pos. 3 CH2), 1.85 – 1.76 (m, 2H,Cy Pos. 4 CH2), 1.56 – 1.34 (m, 34H, Pip Pos. 2 + Pos. 3 CH2 + Cy Pos. 4 CH2 + iPr CH3). 13C NMR (101 MHz, C6D6): δ = 48.8 (d, 2JCP = 5.9 Hz, Pip Pos. 1 CH2), 37.8 (dd, 1JCP = 31.4, 3JCP = 17.3 Hz, Cy Pos. 1 CH), 33.7 (dd, 2JCP = 16.5, 4JCP = 10.0 Hz, Cy Pos. 2 CH2), 31.9 (dd, 2JCP = 13.3, 1.9 Hz, iPr CH), 30.0 (dd, 1JCP = 177.3, 29.3 Hz, P-C--P), 28.6 (dd, 3JCP = 24.6, 10.5 Hz, Cy Pos. 3 CH2), 27.7 (s, Pip Pos. 2 CH2), 27.0 (d, 4JCP = 4.7 Hz, Cy Pos. 4 CH2), 26.3 (d, 3JCP = 7.7 Hz, iPr CH3), 25.6 (s, Pip Pos. 3 CH2). 31P NMR (162 MHz, C6D6): δ = 61.2 (d, 2JPP = 215.8 Hz, P(Pip)3), -0.3 (d, 2JPP = 215.9 Hz, PCy2). IR (ATR) [cm-1]: 3676 (w), 3399 (w), 2914 (w), 2839 (w), 1637 (w), 1437 (w), 1324 (w), 1204 (w), 1153 (w), 1110 (w), 1041 (w), 1021 (w), 938 (vs), 850 (w), 695 (w), 664 (w), 592 (w), 553 (w), 530 (w), 462 (w). Melting point: 143.0 °C (decom- position). HRMS (ESI): m/z C31H60N3P2 [M+H]+ Calculated: 536.4257 Found: 536.4253. Synthesis of L6: 1.92 g (4.36 mmol, 1 eq.) phosphonium salt 2·H2 was sus- pended in THF and deprotonated by slow addition of of 2.81 ml of a n-BuLi solution (1.55 M in hexane, 4.36 mmol, 1 eq.) until a clear, slightly yellow solution was formed. The solution was stirred for 45 min and then 0.43 ml ditertbutylchlorophosphine (2.18 mmol, 0.5 eq.) were added at room temperature. The solution was stirred for 16h at reflux, during which time reformed phosphoniumsalt precipitated as a white solid. The solid was filtered off and the solvent of the solution was removed in vacuo. The residue was suspended in 20ml acetonitrile and stirred overnight, forming a colorless solid. The solid was filtered off, washed with acetonitrile 2 x 15 ml and dried in vacuo thus giving L6 (587 mg, 1.29 mmol, 59%) as a colorless solid. 1H NMR (400 MHz, C6D6): δ = 3.04 (q, JHH = 5.1 Hz, 12H, Pip Pos. 1), 1.98 (dd, 3JHP = 15.4, 3.0 Hz, 3H, P-C--CH3), 1.53 (d, 3JHP = 10.8 Hz, 18H, tBu CH3), 1.30 - 1.45 (m, 18H, Pip Pos. 2 + Pos. 3 CH2). 13C NMR (101 MHz, C6D6): δ = 47.9 (d, 2JCP = 4.8 Hz, Pip Pos. 1 CH2), 36.0 (dd, 1JCP = 23.4 Hz, 3JCP = 10.7 Hz, tBu C(CH3)3), 33.0 (d, 2JCP = 15.2 Hz, tBu C(CH3)3), 27.1 (d, 3JCP = 5.0 Hz, Pip Pos. 2 CH2), 25.5 (d, 4JCP = 1.2 Hz, Pip Pos. 3 CH2), 17.5 (d, 2JCP = 9.9 Hz, P-C--CH3), 16.9 (dd, 1JCP = 191.5, 25.3 Hz, P-C--P). 31P NMR (162 MHz, C6D6): δ = 60.8 (d, 2JPP = 208.5 Hz, P(Pip)3), 25.3 (d, 2JPP = 208.9 Hz, PtBu2). IR (ATR) [cm-1]: 3998 (w), 3933 (w), 3903 (w), 3870 (w), 3802 (w), 3750 (w), 3388 (w), 2924 (m), 2848 (w), 1636 (w), 1439 (w), 1356 (w), 1322 (w), 1258 (w), 1213 (m), 1153 (s), 1119 (w), 1052 (vs), 939 (vs), 888 (s), 854 (m), 808 (m), 696 (m), 587 (m), 545 (m). Melting point: 147.8 °C. HRMS (ESI): m/z C25H52N3P2 [M+H]+ Calculated: 456.3631 Found: 456.3625. Synthesis of L7: 6.5 g (12.6 mmol, 1 eq.) Phosphonium salt 7·H2 was sus- pended in 70 ml THF and deprotonated by slow addition of 8.4 ml of a n-BuLi solution (1.5 M in hexane, 12.6 mmol, 1 eq.) until a clear, slightly yellow solution was formed. The solution was stirred for 45 min and then 3.34 ml of dicyclohexyliodophosphine (15.1 mmol, 1.1 eq.) were added at room temperature. A colorless solid precipitated shortly after addition. The suspension was stirred for 2h and then 8.4 ml of a n-BuLi solution (1.5 M in hexane, 12.6 mmol, 1 eq.) were slowly added until a clear, yellow solution was formed. The solution was stirred for 30 min and the sol- vent was subsequently removed in vacuuo. The residue was suspended in 75 ml acetonitrile and stirred overnight, forming a colorless solid. The solid was filtered off, washed with acetonitrile 5 x 15 ml, and dried in vacuo thus giving L7 (5 g, 8.65 mmol, 69%) as a colorless solid. 1H NMR (400 MHz, C6D6): δ = 7.49 – 7.41 (m, 1H, Tol. Pos. 6 CH), 7.31 – 7.26 (m, 1H, Tol. Pos. 4 CH), 7.20 – 7.13 (m, 1H, Tol, Pos. 3 CH), 7.13 – 7.07 (m, 1H, Tol. Pos. 5 CH), 2.94 (q, JHH = 4.7 Hz, 12H, Pip Pos. 1 CH2), 2.71 (s, 3H, Tol CH3), 2.53 – 2.45 (m, 2H, Cy Pos. 2 CH2), 2.00 – 1.87 (m, 4H, Cy Pos. 1 CH + Pos. 3 CH2), 1.78 – 1.71 (m, 4H, Cy Pos. 4 CH2), 1.69 – 1.64 (m, 2H, Cy Pos. 3 CH2), 1.59 – 1.30 (m, 28H, Pip Pos. 2 + Pip Pos. 3 + Cy Pos. 2 + Cy Pos. 3 CH2). 13C NMR (101 MHz, C6D6): δ = 143.3 (dd, 2JCP = 12.7, 2.7 Hz, Tol. Pos. 1 C), 142.0 (d, 3JCP = 8.0 Hz, Tol. Pos. 2 C), 138.2 (d, 3JCP = 5.6 Hz, Tol. Pos. 6 CH), 130.3 (s, Tol. Pos. 4 CH), 124.7 (d, 4JCP = 2.7 Hz, Tol. Pos. 3 CH), 124.6 (d, 4JCP = 2.4 Hz, Tol. Pos. 5 CH), 47.9 (d, 2JCP = 3.8 Hz, Pip Pos. 1 CH2), 39.0 (dd, 1JCP = 16.1 Hz, 3JCP = 7.9 Hz, Cy Pos. 1 CH), 34.7 (d, 2JCP = 22.4 Hz, Cy Pos. 2 CH2), 30.8 (d, 3JCP = 7.3 Hz, Cy Pos. 3 CH2), 30.0 (dd, 1JCP = 186.6, 28.5 Hz, P-C--P), 29.1 (d, 3JCP = 13.6 Hz, Cy Pos. 3 CH2), 27.5 (s, Cy Pos. 4 CH2) , 26.8 (d, 3JCP = 5.4 Hz, Pip Pos. 2 CH2), 25.5 (s, Pip Pos. 3 CH2), 22.9 (s, Tol. CH3). 31P NMR (162 MHz, C6D6): δ = 51.6 (d, 2JPP = 160.3 Hz, P(Pip)3), -1.3 (d, 2JPP = 160.0 Hz, PCy2). IR (ATR) [cm-1]: 2924 (m), 2843 (m), 1590 (w), 1476 (w), 1442 (w), 1371 (w), 1328 (w), 1208 (m), 1154 (w), 1116 (m), 1057 (s), 1015 (m), 939 (vs), 899 (w), 852 (w), 787 (w), 733 (w), 696 (w), 583 (w), 549 (m), 508 (w), 471 (m), 414 (m). Melting point: 151.7 °C (decomposition). HRMS (ESI): m/z C35H60N3P2 [M+H]+ Calculated: 584.4257 Found: 584.4249. Synthesis of L8: 3.8 g (8.64 mmol, 1 eq.) phosphonium salt 2·H2 was suspended in 25 ml THF and deprotonated by slow addition of 5.72 ml of a n-BuLi solution (1.51 M in hexane, 8.64 mmol, 1 eq.) until a clear, slightly yellow solution was formed. The solution was stirred for 45 min and then a solution of 1.5 g diadamantylchlorophosphine (4.32 mmol, 0.5 eq.) in 10 ml THF was added at room temperature. The solution was stirred for 16h at reflux, during which time reformed phosphoniumsalt precipitated as a white solid. The solid was filtered off and the solvent of the solution was removed in vacuo. The residue was suspended in 25 ml acetonitrile and stirred overnight, forming a colorless solid. The solid was filtered off, washed with acetonitrile 2 x 15 ml and dried in vacuo thus giving L8 (1.87 g, 4.32 mmol, 71%) as a colorless solid. IR (ATR) [cm1]: 2898 (m), 2844 (w), 2673 (w), 1447 (w), 1368 (w), 1325 (w), 1258 (w), 1213 (w), 1154 (w), 1118 (w), 1058 (m), 1024 (w), 933 (vs), 884 (m), 809 (w), 693 (m), 667 (w), 558 (w), 466 (m), 423 (m). Melting point: 179.9 °C (decomposition). 3.0 g (5.82 mmol, 1 eq.) Phosphonium salt 7·H2 was sus- pended in 20 ml THF and deprotonated by slow addition of 3.88 ml of a n-BuLi solution (1.6 M in hexane, 5.82 mmol, 1 eq.) until a clear, slightly yellow solution was formed. The so- lution was stirred for 45 min and then 1.02 ml of diisopropyliodophosphine (6.4 mmol, 1.1 eq.) were added at room temperature. A colorless solid pre- cipitated shortly after addition. The suspension was stirred for 2h and then 3.88 ml of a n-BuLi solution (1.6 M in hexane, 5.82 mmol, 1 eq.) were slowly added until a clear, yellow solution was formed. The solution was stirred for 30 min and the solvent was subsequently removed in vacuo until ~3ml re- mained. To the residue 40 ml acetonitrile were added and it was stirred over- night, forming a colorless solid. The solid was filtered off, washed with ace- tonitrile 5 x 5 ml, and dried in vacuo thus giving L9 (1.71 g, 3.39 mmol, 59%) as a colorless solid. General Procedure for the Synthesis of L10-L17: The phosphonium salt (1 eq.) was suspended in THF (75 ml). A solution of n-BuLi in hexane (1.6 M, 1 eq.) was added slowly. After stirring the solution for 1 h at room temperature, dialkyliodophosphine (1.2 eq.) in pentane (75 ml) was added. The reaction mixture was stirred for 2 h and the formed colorless precipitate was filtered off and washed with pentane (3 x 20 ml). The solid was dried in vacuo, KOtBu (1.5 eq) was added and the mixture was stirred in toluene (100 ml) overnight. The solvent was removed in vacuo and the residue was resuspended in pentane (200 ml). The mixture was filtered over a Celite plug and the residue was extracted with pentane (3 x 50 ml). The solvent was removed in vacuo and the residue was stirred in acetonitrile (150 ml) until a finely dispersed colorless solid was obtained. The colorless solid was filtered off and washed with acetonitrile (3 x 50 ml) to obtain the product. Phosphine L10 was synthesized from 10·H2 (2.02 g, 4.67 mmol) according to the general procedure for P,N-YPhos ligands. Colorless crystals suitable for single crystal X-ray dif- fraction experiments were obtained by slow evaporation of a saturated benzene solution. Yield: (1.25 g, 2.50 mmol, 54%). 7.37 (d, 3JHH = 7.6 Hz, 1H, oTolortho), 7.25 (d, 3JHH = 7.4 Hz, 1H, oTolmeta), 7.14 – 7.04 (m, 2H, oTolmeta’+para), 2.80 – 2.67 (m, 3H, NC2H4N+Cy, H1), 2.67 – 2.62 (m, 5H, NC2H4N+CH3), 2.50 (d, 3JHP = 8.9 Hz, 6H, NCH3), 2.38 – 2.26 (m, 2H, Cy, H2), 2.01 – 1.82 (m, 6H, PCy2, H1+2+3), 1.81 – 1.67 (m, 6H, PCy2, H3+4+Cy, H3), 1.67 – 1.59 (m, 2H, PCy2, H2), 1.59 – 1.25 (m, 11H, Cy, H2+3+4, PCy2, H2+3+4), 1.18 – 1.01 (m, 5H, Cy, H4, PCy2, H2+3+4) ppm. 142.6 (dd, 2JCP = 9.7, 4.3 Hz, oTolipso), 140.4 (d, 3JCP = 7.0 Hz, oTolortho), 137.2 (d, 3JCP = 6.8 Hz, oTolortho’), 130.6 (d, 4JCP = 1.7 Hz, oTolmeta), 124.9 (t, J = 2.4 Hz, oTolmeta+para), 48.5 (d, 2JCP = 4.7 Hz, NC2H4N), 39.0 (dd, 1JCP = 85.6, 3JCP = 13.8 Hz, Cy, C1), 37.2 (brs, PCy2, C1), 34.0 (dd, 1JCP = 134.3, 31.8 Hz, PCP), 33.9 (d, 2JCP = 6.0 Hz, NCH3), 32.8 (d, 2JCP = 18.6 Hz, Cy, C2), 30.9 (d, 3JCP = 9.6 Hz, PCy2, C3), 28.7 – 28.4 (m, PCy2, C2+3), 28.2 (d, 3JCP = 7.8 Hz, Cy, C3), 27.5 (s, PCy2, C4), 27.2 (d, 2JCP = 13.4 Hz, PCy2, C2), 26.7 (d, 4JCP = 1.5 Hz, Cy, C4), 22.6 (s, CH3, oTol) ppm. 31P{1H} NMR (162 MHz, C6D6): δ = 57.8 (d, 2JPP = 161.3 Hz, PCy(MeNC2H4NMe)), -1.9 (d, 2JPP = 161.3 Hz, PCy2) ppm. IR (ATR): 2919 (s), 2844 (s), 1445 (m), 1236 (m), 1163 (m), 1108 (w), 1023 (s), 996 (m), 940 (s), 911 (m), 886 (m), 849 (m), 728 (s), 679 (m), 665 (m), 634 (w), 544 (m), 488 (m), 468 (m), 430 (w) cm-1. Melting point: 121 °C. Elemental analysis for C30H50N2P2: calculated: C 71.97; H 10.07; N 5.59, found: C 72.06; H 10.29; N 5.56. Synthesis of L11: Phosphine L11 was synthesized from 11·H2 (12.25 g, 25.1 mmol) according to the general procedure for P,N-YPhos ligands. Colorless crystals suitable single crystal X-ray diffraction experiments were obtained by slow evaporation of a saturated benzene solution. Yield: (12.4 g, 22.2 mmol, 88%). NMR spectroscopy was performed at 70 °C. 1H NMR (400 MHz, C6D6): δ = 7.36 (d, 3JHH = 7.5 Hz, 1H, oTolortho), 7.13 (d, 3JHH = 6.4 Hz, 1H, oTolmeta), 7.06 – 6.93 (m, 2H, oTolmeta’+para), 3.85 – 3.71 (m, 2H, NCH(CH3)2), 2.85 – 2.62 (m, 5H, NC2H4N+Cy, H1), 2.57 (s, 3H, CH3, oTol), 2.40 – 2.30 (m, 2H, Cy, 2), 2.19 (s, 2H, Cy, 2), 1.95 – 1.81 (m, 4H, Cy, 3+PCy2, H1), 1.73 – 1.06 (m, 24H, Cy+PCy2), 1.01 (d, 3JHH = 6.6 Hz, 6H, CH3, iPr), 0.90 – 0.75 (m, 6H, CH3, iPr) ppm. 143.9 (dd, 2JCP = 6.7, 3.4 Hz, oTolipso), 140.7 (d, 3JCP = 9.8 Hz, oTolortho), 136.0 (d, 3JCP = 7.3 Hz, oTolortho’), 130.6 (s, oTolpara), 124.8 (d, 4JCP = 1.5 Hz, oTolmeta), 124.4 (d, 4JCP = 2.0 Hz, oTolmeta’), 43.9 (dd, 2JCP = 7.1 Hz, 4JCP = 2.2 Hz, NCH(CH3)2), 40.2 (dd, 1JCP = 88.9 Hz, 3JCP = 12.8 Hz, Cy, C1), 39.2 (brs, PCy2, C1), 38.8 (d, 2JCP = 6.1 Hz, NC2H4N), 34.6 (dd, 1JCP = 122.4, 31.1 Hz, PCP), 34.6 (d, 2JCP = 22.9 Hz, Cy, C2), 30.9 (d, 3JCP = 6.8 Hz, PCy2, C3), 29.1 – 28.8 (m, PCy2, C2+3), 28.3 (d, 3JCP = 5.9 Hz, Cy, C3), 27.6 – 27.4 (m, PCy2, C2+4), 27.0 (d, 4JCP = 1.6 Hz, Cy, C4), 22.2 (s, CH3, oTol), 21.6 (d, 3JCP = 2.4 Hz, CH3, iPr), 21.1 (d, 3JCP = 3.6 Hz, CH3, iPr) ppm. 31P{1H} NMR (162 MHz, C6D6): δ = 59.5 (d, 2JPP = 168.2 Hz, PCy(iPrNC2H4NiPr)), 0.8 (d, 2JPP = 168.2 Hz, PCy2) ppm. IR (ATR): 2913 (s), 2846 (m), 1447 (w), 1363 (w), 1213 (w), 1175 (m), 1102 (m), 1057 (s), 1011 (m), 992 (m), 900 (m), 883 (m), 849 (w), 726 (s), 683 (w), 577 (w), 545 (s), 535 (w), 509 (s), 465 (w) cm-1. Melting point: 174 °C. Elemental analysis for C34H58N2P2: calculated: C 73.34; H 10.50; N 5.03, found: C 72.98; H 10.67; N 4.96. Synthesis of L12: Phosphine L12 was synthesized from 12·H2 (8.23 g, 15.1 mmol) according to the general procedure for P,N- YPhos ligands. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow evap- oration of a saturated hexane solution. Yield: (7.51 g, 12.25 mmol, 81%). NMR spectroscopy was performed at 70 °C. 1H NMR (400 MHz, C6D6): δ = 7.42 (d, 3JHH = 7.5 Hz, 1H, oTolortho), 7.20 (d, 3JHH = 7.4 Hz, 1H, oTolmeta), 7.09 (t, 3JHH = 7.2 Hz, 1H, oTolmeta’), 7.03 (t, 3JHH = 7.3 Hz, 1H, oTolpara), 3.31 – 3.17 (m, 2H, NCH2), 3.02 – 2.83 (m, 6H, NCH2+NC2H4N), 2.67 (s, 4H, CH3, oTol+Cy, H1), 2.42 – 2.34 (m, 2H, Cy, H2), 2.06 – 1.85 (m, 6H, PCy2, ), 1.78 – 1.61 (m, 8H, Cy, H3+PCy2, H2+3), 1.60 – 1.06 (m, 22H, Cy/PCy2), 0.94 (dd, 3JHH = 6.6, 2.7 Hz, 12H, CH3, iPen) ppm. δ = 143.2 (dd, 2JCP = 10.8, 3.8 Hz, oTolipso), 140.5 (d, 3JCP = 8.0 Hz, oTolortho), 137.0 (d, 3JCP = 6.8 Hz, oTolortho’), 130.66 (d, 4JCP = 0.9 Hz, oTolmeta), 125.1 (d, 4JCP = 1.7 Hz, oTolmeta’), 124.8 (d, 5JCP = 2.3 Hz, oTolpara), 46.1 (dd, 2JCP = 4.8 Hz, 4JCP = 1.2 Hz, NCH2), 45.8 (dd, 2JCP = 5.2 Hz, 4JCP = 1.9 Hz, NC2H4N), 40.20 (dd, 1JCP = 86.3 Hz, 3JCP = 12.7 Hz, Cy, C1), 38.6 (d, 3JCP = 5.4 Hz, CH2, iPen), 38.1 (dd, 1JCP = 15.5 Hz, 3JCP = 8.1 Hz, PCy2, C1), 35.5 (dd, 1JCP = 130.3, 31.4 Hz, PCP), 33.9 (d, 2JCP = 21.5 Hz, Cy, C2), 31.0 (d, 3JCP = 8.1 Hz, PCy2, C3), 28.9 – 28.6 (m, PCy2, C2+3), 28.2 (d, 3JCP = 6.7 Hz, Cy, C3), 27.6 – 27.3 (m, PCy2, C2+4), 27.2 (s, CH(CH3)2), 26.9 (d, 4JCP = 1.6 Hz, Cy, C4), 23.0 (s, CH3, iPen), 22.8 (s, CH3, iPen), 22.5 (s, CH3, oTol) ppm. 31P{1H} NMR (162 MHz, C6D6): δ = 59.9 (d, 2JPP = 157.2 Hz, PCy(iP- enNC2H4NiPen)), -0.4 (d, 2JPP = 157.2 Hz, PCy2) ppm. IR (ATR): 2918 (s), 2844 (m), 1442 (w), 1235 (m), 1148 (s), 1122 (w), 1063 (s), 1019 (s), 993 (w), 931 (w), 899 (m), 884 (m), 852 (m), 752 (w), 722 (s), 550 (w), 538 (m), 465 (m) cm-1. Melting point: 140 °C. Elemental analysis for C38H66N2P2: calculated: C 74.47; H 10.85; N 4.57, found: C 74.62; H 11.23; N 4.54. L13 was synthesized from 13·H2 (10.8 g, mmol) according to the general procedure for P,N-YPhos Colorless crystals suitable for single crystal X-ray dif- experiments were obtained by slow evaporation of a hexane solution. Yield: (8.35 g, 15.6 mmol, 67%). 3.18 (dd, 3JHP = 13.8, 5JHP = 7.4 Hz, 2H, NCH2tBu), 2.98 – 2.89 (m, 2H, NC2H4N), 2.84 – 2.76 (m, 2H, NC2H4N), 2.68 (dd, 3JHP = 13.7, 5JHP = 5.2 Hz, 2H, NCH2), 2.64 – 2.52 (m, 3H, Cy, H1+3), 2.28 – 2.21 (m, 2H, PCy2, H3), 2.11 – 1.85 (m, 8H, PCy2, H1+2+3), 1.80 – 1.71 (m, 4H, PCy2, ), 1.68 – 1.57 (m, 3H, Cy, H4+PCy2, ), 1.53 (dd, 3JHP = 16.0, 3.0 Hz, 3H, PCPCH3), 1.50 – 1.14 (m, 13H, Cy, H3+PCy2, H2+3+4), 1.00 (s, 18H, CH3) ppm. 60.1 (d, 2JCP = 4.4 Hz, NCH2tBu), 49.1 (d, 2JCP = 5.6 Hz, NC2H4N), 38.9 (dd, 1JCP = 87.3, 3JCP = 8.8 Hz, Cy, C1), 35.7 (dd, 1JCP = 13.2, 3JCP = 8.1 Hz, PCy2, C1), 33.6 (d, 3JCP = 6.4 Hz, C(CH3)3), 32.8 (d, 2JCP = 19.3 Hz, Cy, C2), 32.1 (d, 3JCP = 8.8 Hz, PCy2, C3), 29.6 – 29.2 (m, C(CH3)3+Cy, C3), 28.4 (d, 3JCP = 7.1 Hz, PCy2, C3’), 28.2 (d, 2JCP = 12.2 Hz, PCy2, C2), 27.6 (s, PCy2, C4), 27.1 (d, 2JCP = 13.7 Hz, PCy2, C2’), 27.0 (d, 4JCP = 1.5 Hz, Cy, C4), 17.2 (dd, 1JCP = 140.1, 3JCP = 24.2 Hz, PCP), 12.7 (dd, 1JCP = 4.4, 3JCP = 1.5 Hz, PCPCH3) ppm. 31P{1H} NMR (162 MHz, C6D6): δ = 79.3 (d, 2JPP = 167.4 Hz, PCy(neoPenNC2H4NneoPen)), -3.9 (d, 2JPP = 167.4 Hz, PCy2) ppm. IR (ATR): 2917 (s), 2845 (s), 1443 (m), 1168 (m), 1140 (m), 1067 (m), 1030 (w), 919 (s), 878 (s), 850 (m), 729 (m), 567 (s), 496 (m), 414 (s) cm-1. Melting point: 144 °C. Elemental analysis for C32H62N2P2: calculated: C 71.60; H 11.64; N 5.22, found: C 71.46; H 11.85; N 5.18. L14 was synthesized from 14·H2 (4.01 g, mmol) according to the general procedure for P,N-YPhos 25 ligands. Colorless crystals suitable for single crystal X-ray dif- fraction experiments were obtained by slow evaporation of a saturated benzene solution. Yield (2.13 g, 3.85 mmol, 54%). NMR spectroscopy was performed at 70 °C. 1H NMR (400 MHz, C6D6): δ = 6.82 (s, 2H, Mesmeta), 6.79 (s, 2H, Mesmeta’), 3.46 – 3.36 (m, 2H, NC2H4N), 3.30 – 3.24 (m, 2H, NC2H4N’), 3.00 – 2.87 (m, 1H, Cy, ), 2.57 (s, 6H, CH3, Mesortho), 2.48 (s, 6H, CH3, Mesortho’), 2.33 – 2.18 (m, 2H, Cy, H2), 2.10 (s, 6H, CH3, Mespara), 2.07 – 1.94 (m, 4H, Cy, H2+CH(CH3)2), 1.78 (dd, 3JHP = 16.9, 2.8 Hz, 3H, PCPCH3), 1.70 – 1.54 (m, 3H, Cy, ), 1.34 – 1.22 (m, 3H, Cy, ), 1.15 (dd, 3JHP = 13.0 Hz, 3JHH = 7.0 Hz, 6H, CH3, iPr), 1.07 (dd, 3JHP = 12.4 Hz, 3JHH = 7.1 Hz, 6H, CH3, iPr) ppm. 13C{1H} NMR (101 MHz, C6D6): δ = 139.9 (d, 2JCP = 5.4 Hz, Mesipso), 138.8 (d, 3JCP = 1.5 Hz, Mesortho), 138.4 (d, 3JCP = 2.0 Hz, Mesortho’), 135.9 (s, Mespara), 130.3 (s, Mesmeta), 130.1 (s, Mesmeta’), 49.8 (d, 2JCP = 7.3 Hz, NC2H4N), 44.9 (dd, 1JCP = 87.2 Hz, 3JCP = 7.4 Hz, Cy, C1), 29.8 (dd, 2JCP = 16.7 Hz, 4JCP = 4.7 Hz, Cy, C2), 28.1 (d, 3JCP = 13.8 Hz, Cy, C3), 26.7 (d, 4JCP = 1.8 Hz, Cy, C4), 26.48 (dd, 1JCP = 140.1, 31.2 Hz, PCP), 24.7 (dd, 1JCP = 15.1 Hz, 3JCP = 9.1 Hz, CH(CH3)2), 21.9 (d, 2JCP = 15.1 Hz, CH3, iPr), 21.5 (d, 2JCP = 17.9 Hz, CH3, iPr), 21.0 (s. CH3, Mesortho), 20.7 (s. CH3, Mespara), 20.4 (s, CH3, Mesortho’), 15.7 (d, 1JCP = 3.0 Hz, PCPCH3) ppm. 31P{1H} NMR (162 MHz, C6D6): δ = 50.2 (d, 2JPP = 176.3 Hz, PCy(MesNC2H4NMes)), 8.3 (d, 2JPP = 176.3 Hz, PiPr2) ppm. IR (ATR): 2915 (m), 2847 (w), 1450 (m), 1235 (m), 1216 (m), 1189 (m), 1153 (m), 1073 (s), 958 (m), 913 (s), 873 (s), 846 (s), 823 (s), 622 (m), 554 (m), 533 (w), 444 (m), 436 (m) cm-1. Melting point: 177 °C. Elemental analysis for C34H54N2P2: calculated: C 73.88; H 9.85; N 5.07, found: C 73.52; H 9.85; N 4.91. L15 was synthesized from 15·H2 (6.51 g, mmol) according to the general procedure for P,N- ligands, with the exception that the phosphonium was deprotonated in toluene. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow evap- oration of a saturated hexane solution. Yield: (4.93 mg, 8.88 mmol, 66%). NMR spectroscopy was performed at 70 °C. NMR spectral assignment in some cases was not possible due to overlapping peaks from the three different cyclohexyl moieties. 1H NMR (400 MHz, C6D6): δ = 7.42 (d, 3JHH = 7.4 Hz, 1H, oTolortho), 7.24 – 7.20 (m, 1H, oTolmeta), 7.11 – 7.01 (m, 2H, oTolmeta’+para), 2.67 (s, 3H, CH3, oTol), 2.61 – 2.51 (m, 7H, CH3, DMCDA+Cy, ), 2.47 – 2.12 (m, 5H, PCy2+ Cy(NCH3)2+Cy), 1.88 – 0.95 (m, 37H, PCy2+ Cy(NCH3)2+Cy) ppm. 142.7 (bs, oTol- ipso), 140.9 (d, 3JCP = 7.4 Hz, oTolortho), 137.9 (d, 3JCP = 6.2 Hz, oTolortho’), 130.6 (d, 4JCP = 1.7 Hz, oTolmeta), 125.0 (d, 4JCP = 2.5 Hz, oTolmeta’), 124.8 (d, 5JCP = 2.0 Hz, oTolpara), 66.0 (s, Cy(NCH3)2, C1), 64.5 (d, 2JCP = 4.1 Hz, Cy(NCH3)2, C1), 39.3 (dd, 1JCP = 82.1 Hz, 3JCP = 13.7 Hz, Cy, C1+PCy2, C1), 36.2 (PCy2, C1), 35.1 (dd, 1JCP = 132.8, 33.1 Hz, PCP), 33.4 (s, Cy(NCH3)2+Cy+PCy2), 32.7 (d, J = 18.2 Hz, Cy(NCH3)2+Cy+PCy2), 32.0 (s, NCH3), 31.4 (d, J = 12.7 Hz, Cy(NCH3)2+Cy+PCy2), 30.5 (d, J = 6.0 Hz, Cy(NCH3)2+Cy+PCy2), 30.0 (t, J = 4.1 Hz, Cy(NCH3)2+Cy+PCy2), 29.9 (d, J = 7.3 Hz, Cy(NCH3)2+Cy+PCy2), 29.5 (d, 2JCP = 5.8 Hz, NCH3), 29.2 – 28.9 (m, Cy(NCH3)2+Cy+PCy2), 28.6 (d, J = 6.5 Hz, Cy(NCH3)2+Cy+PCy2), 28.1 (dd, J = 31.1, 9.9 Hz, Cy(NCH3)2+Cy+PCy2), 27.8 – 27.3 (m, Cy(NCH3)2+Cy+PCy2), 26.8 (d, J = 1.5 Hz, Cy(NCH3)2+Cy+PCy2), 24.9 (d, J = 18.6 Hz, Cy(NCH3)2+Cy+PCy2), 22.8 (s, CH3, oTol) ppm. 31P{1H} NMR (162 MHz, C6D6): δ = 59.4 (d, 2JPP = 152.2 Hz, PCyDMCDA), -0.6 (bq, PCy2) ppm. IR (ATR): 2912 (s), 2848 (m), 1442 (m), 1218 (m), 1185 (s), 1058 (m), 1011 (s), 913 (m), 884 (m), 845 (m), 726 (s), 702 (m), 548 (m), 489 (s), 469 (m) cm-1. Melting point: 145 °C. Elemental analysis for C34H56N2P2: calculated: C 73.61; H 10.17; N 5.05, found: C 73.74; H 10.43; N 5.05. Synthesis of L16: Phosphine L16 was synthesized from 16·H2 (1.44 g, 2.76 mmol) according to the general procedure for P,N- YPhos ligands, with the exception that the filtration through a Celite plug was performed in toluene, because a lack of solubility in pentane was present. Colorless crystals suitable single crystal X-ray diffraction experiments were obtained by slow evaporation of a saturated benzene solution. Yield: (1.14 g, 1.93 mmol, 70%). 7.25 (d, 3JHH = 7.4 Hz, 1H, oTolpara), 7.20 (d, 3JHH = 7.0 Hz, 1H, oTolortho), 7.13 – 7.03 (m, 2H, oTolortho’+meta), 3.37 (t, 3JHH = 4.5 Hz, 12H, Mor, H2), 2.85 (q, 3JHH = 4.6 Hz, 12H, Mor, H3), 2.54 (s, 3H, CH3), 2.36 – 2.26 (m, 2H, Cy, H3), 1.92 – 1.76 (m, 4H, Cy, H1+3), 1.72 – 1.67 (m, 3H, Cy, H2+4), 1.63 – 1.52 (m, 2H, Cy, H2), 1.45 – 1.12 (m, 10H, Cy, H2+3+4) ppm. 142.2 (dd, 2JCP = 12.5, 2.0 Hz, oTolipso), 141.4 (d, 5JCP = 8.0 Hz, oTolpara), 137.4 (d, 3JCP = 6.0 Hz, oTolortho), 130.7 (d, 4JCP = 1.5 Hz, oTolmeta), 125.1 (dd, 3JCP = 5.2 Hz, 4JCP = 2.5 Hz, oTolortho’+meta’), 67.2 (d, 2JCP = 5.8 Hz, Mor, C2), 47.4 (d, 3JCP = 3.8 Hz, Mor, C3), 38.8 (dd, 1JCP = 15.3 Hz, 3JCP = 8.0 Hz, Cy, C1), 34.6 (d, 3JCP = 21.9 Hz, Cy, C3), 30.7 (d, 2JCP = 7.3 Hz, Cy, C2), 28.9 (d, 3JCP = 13.8 Hz, Cy, C3), 28.2 (d, 2JCP = 6.0 Hz, Cy, C2), 27.3 (s, Cy, C4), 22.7 (s, CH3) ppm. 31P{1H} NMR (162 MHz, C6D6): δ = 48.6 (d, 2JPP = 161.4 Hz, P(Mor)3), -3.4 (d, 2JPP = 161.4 Hz, PCy2) ppm. IR (ATR): 2915 (w), 2833 (w), 1250 (m), 1128 (w), 1110 (s), 1078 (m), 1006 (w), 990 (w), 946 (s), 917 (w), 889 (m), 847 (w), 722 (m), 706 (m), 540 (w), 501 (m), 490 (m), 464 (m) cm-1. Melt- ing point: 137 °C (decomposition). Elemental analysis for C32H53N3O3P2: calculated: C 65.17; H 9.06; N 7.13, found: C 65.14; H 9.19; N 7.06. Phosphine L17 was synthesized from 17·H2 (1.21 g, (PhNMe)3P 2.39 mmol) according to the general procedure for P,N- P 2C0y2 YPhos ligands, with the exception that Cy2PI was added in pentane (20 ml). Excess THF must be present to dissolve the in situ formed ylide. The filtration through a Celite plug was performed in toluene. Colorless crystals suitable single crystal X-ray diffraction experiments were obtained by slow evaporation of a saturated hexane solution. Yield: (5.67 g, 10.4 mmol, 87%). 7.28 (d, 3JHH = 7.8 Hz, 6H, Phortho), 7.11 (t, 3JHH = 7.9 Hz, 6H, Phmeta), 6.92 (t, 3JHH = 7.4 Hz, 3H, Phpara), 2.74 (d, 3JHP = 7.8 Hz, 9H, CH3NPh), 2.00 – 1.72 (m, 15H, PCy2, H1+2+3+4, PCPCH3), 1.45 – 1.21 (m, 10H, PCy2, H2+3+4) ppm. 147.9 (d, 2JCP = 3.1 Hz, Phipso), 128.8 (s, Phmeta), 127.0 (t, J = 2.5 Hz, Phortho), 124.5 (s, Phpara), 40.9 (t, J = 3.9 Hz, CH3NPh), 36.0 (dd, 1JCP = 14.6, 3JCP = 9.1 Hz, PCy2, C1), 32.5 (d, 2JCP = 18.0 Hz, PCy2, C2), 31.8 (d, 2JCP = 10.8 Hz, PCy2, C2), 28.8 (d, 3JCP = 7.8 Hz, PCy2, C3), 28.3 (d, 3JCP = 11.4 Hz, PCy2, C3), 27.5 (s, PCy2, C4), 19.3 (dd, 1JCP = 202.8, 22.7 Hz, PCPCH3), 15.8 (d, 2JCP = 12.1 Hz, PCPCH3) ppm. 31P{1H} NMR (162 MHz, C6D6): δ = 53.4 (d, 2JPP = 193.3 Hz, P(PhNMe)3), -3.3 (d, 2JPP = 193.3 Hz, PCy2) ppm. IR (ATR): 2918 (m), 2840 (w), 1593 (w), 1489 (m), 1443 (w), 1269 (m), 1172 (w), 1053 (m), 1025 (m), 908 (m), 879 (s), 777 (w), 759 (m), 692 (s), 547 (m), 519 (m), 497 (w), 456 (w) cm-1. Melting point: 152 °C. Elemental analy- sis for C35H49N3P2: calculated: C 73.27; H 8.61; N 7.32, found: C 73.59; H 9.01; N 7.06. Synthesis of L18: NMR (101 MHz, C6D6): δ = 145.9 (d, J = 1.9 Hz, Car.), 142.9 (d, J = 8.8 Hz, Car.), 138.6 (d, J = 2.4 Hz, Car.), 134.4 (d, J = 8.0 Hz, Car.), 131.0 (s, Car.), 129.3 (s, Car.), 127.6 (s, Car.), 126.63 (s, Car.), 126.43 (s, Car.), 124.07 (d, J = 1.8 Hz, Car.), 38.5 (dd, 1JCP = 14.4 Hz, 1JCP = 6.9 Hz, PCy2, C1), 34.4 (d, 2JCP = 20.9 Hz, PCy2, C2), 32.1 (d, 4JCP = 3.3 Hz, CH2, bridge), 30.9 (d, 3JCP = 9.9 Hz, PCy2, C3), 30.6 (dd, 1JCP = 122.9, 29.0 Hz, PCP), 30.3 (d, 1JCP = 7.1 Hz, CH, iPr), 29.6 (d, 1JCP = 7.1 Hz, CH, iPr), 28.7 (d, 2JCP = 13.3 Hz, PCy2, C2), 28.1 (d, 3JCP = 7.1 Hz, PCy2, C3), 27.5 (s, PCy2, C4), 20.7 (dd, 2JCP = 7.1 Hz, 4JCP = 3.4 Hz, CH3, iPr), 19.8 (dd, 2JCP = 5.6 Hz, 4JCP = 2.8 Hz, CH3, iPr) ppm. 31P{1H} NMR (162 MHz, C6D6): 50.88 (d, 2JPP = 142.4 Hz, P(NR2)(iPr)2), -6.86 (d, 2JPP = 142.6 Hz, PCy2) ppm. IR (ATR): 2919 (m), 2848 (w), 1481 (m), 1445 (w), 1282 (w), 1216 (m), 1072 (w), 1025 (w), 989 (m), 908 (m), 865 (w), 845 (w), 749 (s), 696 (s), 559 (s), 489 (w) cm- 1. Melting point: 160 °C. General procedure for the palladium-catalyzed Buchwald-Hartwig-Amination of arylchlorides: A 5 ml screwcap vial with a teflon-coated stir bar and a septum cap was charged in a glovebox with 172 mg (1.5 mmol, 1 eq.) of potassium tert- butoxide. The vial was taken outside of the glovebox and 4 ml of tetrahydro- furan, 0.118 ml (1 mmol, 1 eq.) of 4-chlorotoluene, 0.259 ml tetradecane (1 mmol, 1 eq.) and 1.1 mmol (1.1 eq.) of the amine were added via syringe. A second vial was charged with an equimolar amount of the free ligand and tris(dibenzylideneacetone)dipalladium(0). The catalyst was allowed to pre- form in 0.5 ml of THF and stirred for 30 minutes. The catalyst solution was added to the reaction mixture and stirred at room temperature or at 60 °C. Small aliquots were removed and filtered through silica with ethyl acetate and analyzed by GC/MS and GC/FID. General procedure for the coupling of 4-Chloroanisole with n-BuLi and t- BuLi: The reaction was carried out in 5ml screwcap vials with a teflon-coated stir bar and a septum cap. In a glovebox, the palladium source (0.03 mmol) and ligand (0.03 mmol) were added to the vial. Then, the vial was taken outside of the glovebox and 4-chloroanisole (1 mmol, 142.6 mg), and toluene (1 ml) were added and stirred for 30 min. n-BuLi (1.6 M in hexanes, 1.2 mmol, 0.75 ml) was diluted with toluene to a final volume of 3.3 ml and added over 1 h at room temperature using a syringe pump. The reaction was quenched with the addition of 0.1 ml of water. Small aliquots were removed and filtered through silica with ethyl acetate and analyzed by GC/MS and GC/FID. General procedure for the coupling of 4-Chlorotoluene with Acetone: A 5 ml screwcap vials with a teflon-coated stir bar and a septum cap was charged in a glovebox with base. The vial was taken outside of the glovebox and Acetone, Arylchloride (1 mmol, 1 eq.) and 0.259 ml tetradecane (1 mmol, 1 eq.) were added via syringe. A second vial was charged with an equimolar amount of the free ligand and palladium source. The catalyst was allowed to preform in 0.5 ml of THF and stirred for 15 minutes. The catalyst solution was added to the reaction mixture and stirred at room temperature for 16h. Small aliquots were removed and filtered through silica with ethyl acetate and analyzed by GC/MS and GC/FID. General procedure for gold-catalyzed hydroamination: A 2 mL screwcap vials with a teflon-coated stir bar and a septum cap was charged in a glovebox with 0.005 mmol of LAuCl and NaBArF. The amine (5.25 mmol) and the alkyne (5.00 mmol) were added via syringe. The vial was heated on a hotplate to the indicated temperature while stirring. Small ali- quots were removed via a syringe and added directly to an NMR tube to mon- itor the reaction progress. Yields were calculated by integration of the peak for the alkyne starting material with respect to the peak for the imine product in the 1H-NMR spectrum. General procedure for the hydrogenation of Arylchlorides: 0.03 mmol of Pd2(dba)3 was weighed inside a Schlenk tube and 2 mL THF was added. Subsequently 0.03 mmol of ligand was added and the reaction was allowed to proceed for 30 minutes to generate the active catalyst.1 mmol each of the halo compound and internal standard was added to the reaction mixture and stirred for 2 more hours. Finally 0.05 mmol of sodium tetra- fluoroborate and 1 mmol of potassium phosphate was added and the reaction vessel was degassed via three freeze-pump-thaw cycles. After the third freeze-pump-thaw cycle, hydrogen was introduced into the reaction mixture and the After the Schlenk tube was warmed to 23 °C, the tube was sealed, and the reaction mixture was stirred vigorously at 50°C. After 24 hours, the reaction mixture was opened to air and diluted with ethyl acetate (3 mL) and an aliquot was analyzed by GC or GCMS analysis. General procedure for the coupling of 4-Chlorotoluene with Ammonia: The reaction was performed in screwcap vials with septum caps. In a glove- box, the Pd2dba3 (0.0125 mmol Pd) and ligand (0.0125 mmol) were added to a vial. Next, THF (0.5 ml) was added and the mixture was stirred for 30 min. Another vial was charged with KOtBu (57.3 mg, 0.5 mmol) and 4-chlorotolu- ene (31.6 mg, 29.6 µl, 0.25 mmol), tetradecane (49.6 mg, 6.47 µl, 0.25 mmol) and 1,4-dioxane (2.5 ml) were subsequently added via syringe outside the glovebox. The catalyst stock solution was added to the vial, fol- lowed by the addition of ammonia in dioxane (0.5 M, 2 ml, 1 mmol) and the mixture was heated to 110 °C in a temperature-controlled aluminum heating block for 5 h. Small aliquots were removed, filtered through silica with ethyl acetate as eluent and were analyzed by GC-FID. Results of Buchwald-Hartwig-Amination Table 1: Results of Buchwald-Hartwig amination reactions:
Cond. A: 1 mmol ArCl, 1.1 eq. Amine, 1.5 eq. KOtBu, 0.5 mol% Pd & Ligand, rt, THF; Cond. B: 1 mmol ArCl, 1.1 eq. Amine, 1.5 eq. KOtBu, 1 mol% Pd & Ligand, rt, THF; Cond. C: 1 mmol ArCl, 1.1 eq. Amine, 1.5 eq. KOtBu, 0.5 mol% Pd & Ligand, 50 °C, THF. 5 Results of arylation of ammonia reactions Ligandsd L1 L2 L3 L4 L5 L6 L7 L8 0.0 6.4 9.6 5.0 21.9 42.6 0.0 8.8 36.2 3.9 19.8 9.6 Table 1: Ligand screening results of the monoarylation of ammonia (1 mmol) with 4-chlorotoluene (0.25 mmol), using KOtBu (0.5 mmol), L∙Pd2dba3 (5 mol%) in 1,4-dioxane at 110 °C. Yields are GC-FID yields after 20 5 h with n-tetradecane as internal standard and normalization to the sum of all peaks. Yield of ArNH2 Yield of Ar2NH Ligand conversion (%) (%) (%) L10 100 3 46 L11 100 62 17 L12 100 34 32 L13 100 0 48 L14 3 0 0 L15 100 5 47 L16 100 49 25 L17 78 12 28
Results of coupling of organo-lithium reagents with arylchlorides Table 2: Results of coupling of organo-lithium reagents with arylchlorides: Lig- nBuLi tBuLia) and ArR ArH ArCl ArR ArH ArCl L1 38.0 8.3 53.7 59.0 33.2 7.8 L2 44.8 6.5 48.6 68.3 31.7 0.0 L3 28.7 3.1 68.1 78.8 15.1 6.1 L4 2.7 2.1 95.2 83.2 16.8 0.0 L5 46.1 10.2 43.7 34.8 57.8 7.3 L6 28.8 13.5 57.7 5.7 90.4 3.9 L7 85.7 9.6 4.7 63.6 36.4 0.0 L8 42.4 13.4 44.3 2.6 88.7 8.7 Reaction conditions: 1 mmol ArCl, 1.1 eq. RLi, in Toluene at rt. Addition of R- Li over the period of 1 h. Yields determined by calibrated GC analysis using tetradecane as internal standard. a) only isomerization product observed.
Results of arylation of acetone reactions: Table 3: Screening of reaction conditions Pd Ace- N Lig- Base conc. Pd Pd/L loa- Yiel Base tone o and eq. [M] Source ratio ding/ d eq. mol% 1 L1 Cs2CO3 2 20 0.5 Pd2(dba)3 1/1.25 0.5 2.1 2 L2 Cs2CO3 2 20 0.5 Pd2(dba)3 1/1.25 0.5 31.8 3 L3 Cs2CO3 2 20 0.5 Pd2(dba)3 1/1.25 0.5 3.6 4 L4 Cs2CO3 2 20 0.5 Pd2(dba)3 1/1.25 0.5 0.0 5 L5 Cs2CO3 2 20 0.5 Pd2(dba)3 1/1.25 0.5 4.4 6 L6 Cs2CO3 2 20 0.5 Pd2(dba)3 1/1.25 0.5 22.1 7 L7 Cs2CO3 2 20 0.5 Pd2(dba)3 1/1.25 0.5 68.1 8 L8 Cs2CO3 2 20 0.5 Pd2(dba)3 1/1.25 0.5 9.9 9 L7 K2CO3 2 20 0.5 Pd2(dba)3 1/1.25 0.5 2.3 10 L7 K3PO4 2 20 0.5 Pd2(dba)3 1/1.25 0.5 45.5 11 L7 NaOH 2 20 0.5 Pd2(dba)3 1/1.25 0.5 35.8 12 L7 CsF 2 20 0.5 Pd2(dba)3 1/1.25 0.5 1.7 Na- 13 t 0.5 L7 O Bu 2 20 0.5 Pd2(dba)3 1/1.25 29.3 14 L7 KOtBu 2 20 0.5 Pd2(dba)3 1/1.25 0.5 23.6 15 L7 Cs2CO3 1 20 0.5 Pd2(dba)3 1/1.25 0.5 52.4 16 L7 Cs2CO3 2 20 0.5 Pd2(dba)3 1/1.25 0.5 68.1 17 L7 Cs2CO3 3 20 0.5 Pd2(dba)3 1/1.25 0.5 88.0 18 L7 Cs2CO3 2 10 0.05 Pd2(dba)3 1/1.25 0.5 5.2 19 L7 Cs2CO3 2 20 0.2 Pd2(dba)3 1/1.25 0.5 39.0 20 L7 Cs2CO3 2 10 0.5 Pd2(dba)3 1/1.25 0.5 27.7 21 L7 Cs2CO3 2 50 0.25 Pd2(dba)3 1/1.25 0.5 73.1 22 L7 Cs2CO3 3 50 0.25 Pd2(dba)3 1/1.25 0.5 90.8 Pd(cod) 23 Cs2CO3 0.5 L7 3 50 0.25 Cl2 1/1.25 30.4 Pd(OAc) 24 Cs2CO3 0.5 L7 3 50 0.25 2 1/1.25 40.3 [Pd(al- 25 Cs2CO3 0.5 L7 3 50 0.25 lyl)Cl]2 1/1.25 >99 [Pd(cin) 26 Cs2CO3 0.5 L7 3 50 0.25 Cl]2 1/1.25 88.1 [Pd(ind) 27 Cs2CO3 0.5 L7 3 50 0.25 Cl]2 1/1.25 81.5 28 [Pd(al- Cs2CO3 a) L7 3 50 0.25 lyl)Cl]2 1/1.25 0.2 92.0 29 [Pd(al- 0.2 Cs2CO3 b) L7 3 50 0.25 lyl)Cl]2 1/1.25 87.2 30 [Pd(al- 0.2 Cs2CO3 c) L7 3 50 0.25 lyl)Cl]2 1/1.25 72.1 31 [Pd(al- 0.2 Cs2CO3 d) L7 3 50 0.25 lyl)Cl]2 1/1.25 >99 32 [Pd(al- 0.2 Cs2CO3 e) L7 3 50 0.25 lyl)Cl]2 1/1.25 89.3 [Pd(al- 0.2 33 Cs2CO3 L7 3 50 0.25 lyl)Cl]2 1/0.5 57.1 [Pd(al- 0.2 34 Cs2CO3 L7 3 50 0.25 lyl)Cl]2 1/1.0 97.7 [Pd(al- 0.2 35 Cs2CO3 L7 3 50 0.25 lyl)Cl]2 1/1.5 >99 [Pd(al- 0.2 36 Cs2CO3 L7 3 50 0.25 lyl)Cl]2 1/4.0 >99 37 [Pd(al- 0.2 Cs2CO3 f) L7 3 50 0.25 lyl)Cl]2 1/1.0 33.0 Reaction conditions: 1 mmol ArCl, rt, 16h. Yields determined by calibrated GC analysis using tetradecane as internal standard. a) no catalyst prefor- mation, b) preformation in THF with ArCl for 15 min, c) preformation in THF with ArCl for 1h, d) preformation in THF without ArCl for 15 min, e) prefor- mation in THF without ArCl, f) wet, technical grade Acetone and reaction under air. Scope: 92% 94% 90% 91% Reaction conditions: 1 mmol ArCl, 3 eq. Cs2CO3, in 3.7 ml Acetone, 0.1 mol% [Pd(allyl)Cl]2, 0.2 mol% L7, rt, 16h, yields of isolated product. Results of the Hydrogenation reactions of arylhalides: Table 5: Results of the hydrogenation reactions of arylhalides 50 °C 60 °C 4-Bromoacetophenone 4-Bromoacetophenone L1 35% n.d. L2 59% n.d. L7 82% 88% 4-Chloranisole 4-Chloranisole L7 66% 72% Reaction conditions: 1 mmol ArCl, 3 mol% Pd2dba3, 3 mol% L, 15 mol% NaBF4, 1 mmol K3PO4, in THF at 50 or 60 °C under 1 atm H2. Synthesis and Characterization of the Products from arylation of Acetone: phenyl)propan-2-one (1) Compound 1 was synthesized according to the general pro- cedure, purified by filtration over silica and isolated in 99 % 15 yield as colorless liquid. The analytical data is in accordance 1H NMR (400 MHz, CDCl3): δ 7.36 (d, J = 8.27 Hz, 2H), 7.14 (d, J = 8.29 Hz, 2H), 3.66 (s, 2H), 2.16 (s, 3H), 1.32 (s, 9H). 13C NMR (101 MHz, CDCl3): δ = 206.9, 150.1, 131.3, 129.2, 125.8, 50.7, 34.6, 31.5, 29.4. IR (cm-1): 2961 (m), 2904 (w), 2869 (w), 1712 (vs), 1514 (m), 1463 (w), 1413 (m), 1362 (m), 1268 (m), 1229 (w), 1158 (m), 1109 (w), 1020 (w), 836 (w), 687 (w), 593 (w), 547 (m), 421 (w). MS (EI): m/z (%) = 190.1 (35.54, [M+]), 175.1 (53.75), 147.7 (100), 133.1 (37.95), 132.1 (30.79), 117.1 (35.9), 105.1 (23.26), 91.0 (21.26). 1-(naphthalen-1-yl)propan-2-one (2) Compound 2 was synthesized according to the general pro- cedure, purified by filtration over silica and isolated in 95 % yield as colorless liquid. The analytical data is in accordance with the reported literature. NMR (400 MHz, CDCl3): δ 7.88 (ddd, J = 6.94, 4.73, 1.99 Hz, 2H), 7.81 (d, J = 8.13 Hz, 1H), 7.52 (ddd, J = 7.21, 4.93, 1.79 Hz, 2H), 7.47 – 7.42 (m, 1H), 7.41 – 7.36 (m, 1H), 4.12 (s, 2H), 2.12 (s, 3H). 13C NMR (101 MHz, CDCl3): δ = 207.1, 134.0, 132.3, 131.2, 128.9, 128.4, 128.2, 126.7, 126.1, 125.7, 124.0, 49.4, 29.1. IR (cm-1): 3046 (w), 2970 (w), 1708 (vs), 1596 (m), 1510 (m), 1397 (m), 1356 (m), 1228 (m), 1163 (m), 1021 (m), 787 (vs), 560 (w), 530 (m), 451 (w), 427 (w). MS (EI): m/z (%) = 115 (41.58), 139.1 (18.12), 141.1 (100), 142.1 (29.51), 184.1 (38.06 [M+]). ethyl 2-(2-oxopropyl)benzoate (3) Compound 3 was synthesized according to the general pro- cedure, purified by column chromatography (Hexane/Ethy- lacetate 20:1) and isolated in 91 % yield as colorless liquid. The analytical data is in accordance with the reported literature.1H NMR (400 MHz, CDCl3): δ = 7.9 (ddd, J = 6.9, 4.7, 2.0 Hz, 2H), 7.8 (d, J = 8.1 Hz, 1H), 7.5 (ddd, J = 7.2, 4.9, 1.8 Hz, 2H), 7.5 – 7.4 (m, 1H), 7.4 – 7.4 (m, 1H), 4.1 (s, 2H), 2.1 (s, 3H). 13C NMR (101 MHz, CDCl3): δ = 209.3, 166.4, 138.5, 130.2, 129.6, 69.8, 61.2, 52.8, 51.5, 29.4, 14.5. IR (cm-1): 2974 (w), 2933 (w), 2770 (w), 1709 (vs), 1610 (w), 1576 (w), 1465 (w), 1417 (w), 1367 (w), 1275 (vs), 1179 (w), 1105 (m), 1066 (w), 1022 (w), 914 (w), 856 (w), 760 (w), 710 (w), 506 (w), 468 (w), 402 (w). MS (EI): m/z (%) = 89.0 (21.28), 90.0 (29.44), 91.0 (27.31), 107.0 (15.74), 118.0 (26.5), 135.0 (28.79), 136.0 (62.39), 161.0 (25.21), 164.1 (100, [M+]). 1-(4-fluorophenyl)propan-2-one (4) Compound 4 was synthesized according to the general pro- cedure. purified by filtration over silica and isolated in 98 % yield as colorless liquid. The analytical data is in accordance with the reported literature. 1H NMR (400 MHz. CDCl3): δ 7.16 (dd. J = 8.48. 5.45 Hz. 2H). 7.02 (t. J = 8.64 Hz. 2H). 3.68 (s. 2H). 2.16 (s. 3H). 19F NMR (75 MHz. CDCl3): δ = - 114.6. IR (cm-1): 3044 (w). 3002 (w). 2901 (w). 1712 (s). 1602 (w). 1508 (vs). 1418 (w). 1357 (w). 1326 (w). 1221 (s). 1157 (m). 1096 (w). 1017 (w). 980 (w). 839 (w). 796 (w). 602 (w). 510 (w). 488 (w). 432 (w). 400 (w). MS (EI): m/z (%) = 83.0 (26.44), 109.0 (100), 110.0 (24.15), 152.0 (26.45, [M+]). 1-(2-fluorophenyl)propan-2-one (5) Compound 5 was synthesized according to the general proce- dure. purified by column chromatography (Hexane/Ethylacetate 20:1) and isolated in 85 % yield as colorless liquid. The analyt- ical data is in accordance with the reported literature. 1H NMR (400 MHz. CDCl3): δ 7.30 – 7.23 (m. 1H). 7.18 (td. J = 7.48. 1.89 Hz. 1H). 7.14 – 7.03 (m. 2H). 3.74 (s. 2H). 2.20 (s. 3H). 13C NMR (101 MHz. CDCl3) δ 205.1. 161.1 (d. J = 245.71 Hz). 131.8 (d. J = 4.21 Hz). 129.2 (d. J = 8.11 Hz). 124.4 (d. J = 3.62 Hz). 121.8 (d. J = 16.19 Hz). 115.6 (d. J = 21.71 Hz). 44.0 (d. J = 2.31 Hz). 29.5. 19F NMR (75 MHz. CDCl3): δ = -115.3. IR (cm- 1): 2999 (w). 2935 (w). 2835 (w). 1708 (vs). 1610 (m). 1578 (w). 1501 (vs). 1464 (w). 1424 (w). 1355 (m). 1302 (w). 1252 (vs). 1217 (w). 1156 (s). 1117 (w). 1043 (s). 927 (w). 874 (w). 809 (m). 706 (w). 533 (m). 476 (w). 453 (w). 409 (w). MS (EI): m/z (%) = 83.0 (33.63), 109.0 (100), 110.0 (26.82), 152.0 (42.04, [M+]). 1-(3-(methylthio)phenyl)propan-2-one (6) Compound 6 was synthesized according to the general pro- cedure. purified by column chromatography (Hex- 20:1) and isolated in 93 % yield as colorless liquid. The an- alytical data is in accordance with the reported literature. 1H NMR (400 MHz. CDCl3): δ 7.25 (t. J = 7.69 Hz. 1H). 7.16 (dt. J = 8.16. 1.47 Hz. 1H). 7.09 (d. J = 1.83 Hz. 1H). 6.97 (dt. J = 7.58. 1.40 Hz. 1H). 3.66 (s. 2H). 2.48 (s. 2H). 2.16 (s. 3H). 13C NMR (101 MHz. CDCl3): δ = 206.2. 139.3. 135.0. 129.3. 127.5. 126.3. 125.3. 51.0. 29.5. 15.9. IR (cm-1): 2920 (w). 1710 (vs). 1591 (m). 1475 (m). 1421 (m). 1356 (m). 1321 (m). 1225 (m). 1157 (m). 1086 (m). 969 (w). 881 (w). 770 (s). 701 (s). 526 (m). 467 (w). 438 (w). MS (EI): m/z (%) = 108.0 (40.65), 112.0 (28.93), 125.0 (49.8), 158.0 (100), 160.0 (38.19, [M+]). 1-chloro-2-methylbenzene (7) Compound 7 was synthesized according to the general procedure. purified by column chromatography (Hexane/Ethylacetate 20:1) and isolated in 73 % yield as colorless liquid. The analytical data is in accordance with the reported literature. 1H NMR (400 MHz. CDCl3) δ 7.22 – 7.16 (m. 3H). 7.16 – 7.12 (m. 1H). 3.71 (s. 2H). 2.25 (s. 3H). 2.14 (s. 3H). 13C NMR (101 MHz. CDCl3): δ = 206.5. 137.0. 133.3. 130.6. 130.5. 127.5. 126.4. 49.3. 29.4. 19.7. IR (cm-1): 3064 (w). 3018 (w). 2918 (w). 1709 (vs). 1604 (w). 1495 (w). 1462 (w). 1420 (w). 1356 (m). 1324 (w). 1227 (w). 1159 (m). 1110 (w). 1052 (w). 741 (s). 636 (w). 567 (w). 515 (w). 469 (w).444 (w). MS (EI): m/z (%) = 77.0 (23.66), 105.1 (100), 106.1 (31.36), 148.1 (38.81, [M+]). 1-(5-methoxy-2-methylphenyl)propan-2-one (8) Compound 8 was synthesized according to the general proce- dure. purified by column chromatography (Hexane/Ethylacetate 20:1) and isolated in 60 % yield as colorless liquid. The analyt- ical data is in accordance with the reported literature. 1H NMR (400 MHz. CDCl3): δ = 7.2 – 7.2 (m. 1H). 7.2 – 7.1 (m. 0H). 3.7 (s. 1H). 2.3 (s. 1H). 2.1 (s. 1H). MS (EI): m/z (%) = 91.0 (22.26), 135.1 (100), 136.1 (22.07), 178.1 (29.6, [M+]). 1-(1-methyl-1H-pyrrolo[2.3-b]pyridin-4-yl)propan-2-one (9) Compound 9 was synthesized according to the general pro- cedure. purified by column chromatography (Hex- ane/Ethylacetate 20:1) and isolated in 78 % yield as colorless liquid. NMR (400 MHz. CDCl3): δ 8.30 (d. J = 4.84 Hz. 1H). 7.19 (d. J = 3.46 Hz. 1H). 6.92 (d. J = 4.83 Hz. 1H). 6.44 (d. J = 3.44 Hz. 1H). 3.94 (s. 2H). 3.89 (s. 3H). 2.14 (s. 3H). 13C NMR (101 MHz. CDCl3): δ 205.1. 147.9. 143.2. 135.5. 129.3. 120.7. 116.7. 97.8. 48.6. 31.6. 29.4. IR (cm-1): 3049 (w). 2913 (w). 1712 (vs). 1585 (m). 1514 (s). 1436 (w). 1406 (m). 1348 (s). 1299 (m). 1210 (w). 1159 (w). 1087 (w). 1030 (w). 1010 (w). 965 (w). 875 (w). 832 (w). 798 (w). 716 (m). 643 (w). 603 (w). 543 (w). 515 (w). 418 (w). HRMS (ESI): m/z C11H13N2O [M+H]+ Calculated: 189.1028 Found: 189.1020. MS (EI): m/z (%) = 117.0 (10.08), 144.1 (17.47), 145.1 (100), 146.1 (79.0), 188.1 (53.04, [M+]). 1-(3.5-dimethoxyphenyl)propan-2-one (10) Compound 10 was synthesized according to the general procedure. purified by column chromatography (Hex- ane/Ethylacetate 20:1) and isolated in 97 % yield as color- less liquid. The analytical data is in accordance with the reported literature. 6.37 (t. J = 2.23 Hz. 3H). 6.35 (d. J = 2.25 Hz. 6H). 3.78 (s. 5H). 3.61 (s. 2H). 2.15 (s. 3H). 13C NMR (101 MHz. CDCl3): δ = 206.4. 161.2. 136.5. 107.6. 99.2. 55.4. 51.5. 29.2. IR (cm-1): 3000 (w). 2939 (w). 2838 (w). 2349 (w). 1711 (m). 1596 (vs). 1463 (m). 1431 (m). 1350 (m). 1293 (w). 1206 (s). 1159 (s). 1068 (m). 927 (w). 836 (w). 704 (w). 529 (w). 487 (w). 459 (w). 421 (w). MS (EI): m/z (%) = 77.0 (23.48), 91.1 (25.95), 151.1 (100), 152.1 (86.0), 194.1 (86.32, [M+]). 1-(3-methylbenzo[b]thiophen-5-yl)propan-2-one (11) Compound 1 was synthesized according to the general pro- cedure. purified by column chromatography (Hex- ane/Ethylacetate 20:1) and isolated in 97 % yield as color- less liquid. NMR (400 MHz. CDCl3): δ 7.81 (d. J = 8.20 Hz. 1H). 7.67 – 7.38 (m. 1H). 7.19 (dd. J = 8.29. 1.69 Hz. 1H). 7.09 (d. J = 1.41 Hz. 1H). 3.84 (s. 2H). 2.43 (d. J = 1.24 Hz. 3H). 2.18 (s. 3H). 13C NMR (101 MHz. CDCl3): δ 206.8. 140.3. 139.2. 132.1. 130.1. 125.7. 123.2. 122.6. 122.4. 51.2. 29.4. 14.0. IR (cm-1): 3076 (w). 2914 (w). 2855 (w). 1709 (vs). 1599 (w). 1558 (w). 1442 (w). 1355 (w). 1318 (w). 1227 (w). 1157 (w). 1090 (w). 1049 (w). 1020 (w). 985 (w). 883 (w). 834 (w). 777 (w). 736 (w). 626 (w). 579 (w). 546 (w). 521 (w). 402 (w). HRMS (ESI): m/z C12H13OS [M+H]+ Calculated: 205.0687 Found: 205.0679. MS (EI): m/z (%) = 115.0 (14.3), 128.0 (9.61), 161.1 (100), 162.0 (16.09), 204.0 (30,0 [M+]). 1-(benzo[d][1.3]dioxol-5-yl)propan-2-one (12) Compound 12 was synthesized according to the general procedure. purified by column chromatography (Hex- 20:1) and isolated in 76 % yield as colorless liquid. The an- alytical data is in accordance with the reported literature. 1H NMR (400 MHz. CDCl3): δ = 6.7 (d. J = 7.82 Hz. 1H). 6.7 (d. J = 1.73 Hz. 1H). 6.6 (dd. J = 7.91. 1.73 Hz. 1H). 5.9 (s. 2H). 3.6 (s. 2H). 2.1 (s. 3H). 13C NMR (101 MHz. CDCl3): δ = 206.6. 147.9. 146.7. 127.9. 122.6. 109.8. 108.5. 101.1. 50.5. 29.1. IR (cm-1): 2995 (w). 2894 (w). 2778 (w). 1708 (s). 1608 (w). 1488 (vs). 1443 (s). 1355 (m). 1246 (vs). 1187 (w). 1159 (m). 1100 (w). 1038 (s). 925 (m). 813 (w). 649 (w). 603 (w). 509 (w). 465 (w). 432 (w). MS (EI): m/z (%) = 51.0 (10.68), 77.0 (20.48), 105.0 (6.36), 135.0 (100), 136.0 (10.03), 178.0 (27.13, [M+]). 2-methyl-1H-indole (13) Compound 13 was synthesized according to the general proce- dure. purified by column chromatography (Hexane/Ethylacetate 20:1) and isolated in 71 % yield as colorless liquid. The analyt- ical data is in accordance with the reported literature. 1H NMR (400 MHz. CDCl3): δ = 7.6 – 7.3 (m. 1H). 7.2 (dd. J = 14.67. 7.20 Hz. 1H). 7.1 – 6.8 (m. 2H). 6.1 (s. 1H). 2.4 (s. 3H). IR (cm-1): 3377 (m). 3052 (w). 2939 (w). 1880 (w). 1800 (w). 1766 (w). 1618 (w). 1580 (w). 1547 (w). 1454 (w). 1401 (w). 1344 (w). 1284 (w). 1216 (w). 1151 (w). 1112 (w). 1036 (w). 1008 (w). 978 (w). 925 (w). 781 (vs). 731 (m). 629 (s). 505 (s). 434 (m). 408 (m). MS (EI): m/z (%) = 64.9 (6.4), 77.0 (11.8), 103.0 (9.21), 130.0 (100), 131.0 (70.17), 132.0 (6.54, [M+]). (4-chlorophenyl)trimethylsilane (14) 14 was synthesized according to the general purified by column chromatography 20:1) and isolated in 92 % yield as (400 MHz. CDCl3): δ = 7.50 (d. J = 7.82 Hz. 2H). 7.20 (d. J = 7.64 Hz. 2H). 3.70 (s. 2H). 2.17 (s. 3H). 0.27 (s. 9H). 13C NMR (101 MHz. CDCl3): δ = 206.4. 139.1. 134.8. 133.9. 128.9. 51.1. 29.4. -1.0. 29Si NMR (80 MHz. CDCl3): δ = -4.05. IR (cm-1): 3067 (w). 3013 (w). 2954 (w). 2896 (w). 1712 (s). 1600 (w). 1554 (w). 1500 (w). 1395 (w). 1356 (w). 1247 (m). 1157 (w). 1106 (m). 838 (vs). 754 (m). 721 (w). 693 (w). 666 (w). 622 (w). 560 (m). 500 (w). 400 (w). IR (cm-1): 73.0 (13.38), 135.0 (19.29), 148.1 (25.03), 163.1 (10.03), 191.1 (100), 192.1 (20.89), 206.1 (51.11, [M+]). 1-(4-benzoylphenyl)propan-2-one (15) Compound 15 was synthesized according to the gen- eral procedure. purified by column chromatography (Hexane/Ethylacetate 20:1) and isolated in 71 % yield as colorless liquid. The analytical data is in accordance with the reported lit- erature. NMR (400 MHz. CDCl3): δ = 7.82 – 7.77 (m. 3H). 7.75 (d. J = 8.23 Hz. 1H). 7.62 – 7.55 (m. 1H). 7.48 (td. J = 7.43. 3.56 Hz. 2H). 7.31 (dd. J = 8.14. 3.87 Hz. 1H). 7.23 (d. J = 8.24 Hz. 1H). 2.63 (s. 2H). 2.17 (s. 3H). 13C NMR (101 MHz. CDCl3): δ = 211.0. 198.7. 139.0. 138.2. 137.8. 132.5. 130.7. 130.2. 130.0. 129.6. 128.4. 53.9. 29.4. IR (cm-1): 2931 (w). 1700 (vs). 1657 (vs). 1605 (m). 1447 (m). 1415 (m). 1362 (m). 1317 (m). 1278 (s). 1178 (m). 1148 (m). 1020 (w). 925 (m). 745 (w). 705 (m). 534 (m). 510 (m). 465 (m). 433 (s). 406 (m). MS (EI): m/z (%) = 77.0 (23.38), 90.0 (20.42), 105.0 (28.96), 118.0 (24.95), 196.1 (100; 197.1 (15.24, [M+]). 1-(4-vinylphenyl)propan-2-one (16) Compound 16 was synthesized according to the general procedure. purified by column chromatography (Hex- ane/Ethylacetate 20:1) and isolated in 90 % yield as colorless liquid. The an- alytical data is in accordance with the reported literature. 1H NMR (400 MHz. CDCl3): δ = 7.38 (d. J = 8.2 Hz. 1H). 7.17 (d. J = 8.1 Hz. 1H). 6.70 (dd. J = 17.6. 10.9 Hz. 1H). 5.74 (d. J = 17.6 Hz. 1H). 5.24 (d. J = 10.9 Hz. 1H). 3.68 (s. 1H). 2.15 (s. 1H). 13C NMR (101 MHz. CDCl3): δ = 206.3. 136.5. 133.9. 129.7. 114.0. 50.8. 29.4. IR (cm-1): 3086 (w). 3005 (w). 2918 (w). 2350 (w). 2304 (w). 2128 (w). 1910 (w). 1822 (w). 1710 (vs). 1630 (w). 1510 (w). 1407 (w). 1356 (w). 1228 (w). 1158 (w). 1114 (w). 991 (w). 909 (w). 845 (w). 802 (w). 721 (w). 647 (w). 601 (w). 539 (w). 477 (w). 413 (w). MS (EI): m/z (%) = 91.0 (18.59), 115.1 (36.12), 117.1 (100), 118.1 (24.45), 160.1 (31.47, [M+]). 1-(4-(dimethylamino)phenyl)propan-2-one (17) Compound 17 was synthesized according to the general procedure. purified by column chromatography (Hex- ane/Ethylacetate 20:1) and isolated in 90 % yield as color- less liquid. The analytical data is in accordance with the reported literature. 1H NMR (400 MHz. CDCl3): δ = 7.07 (d. J = 8.57 Hz. 2H). 6.72 (d. J = 8.30 Hz. 2H). 3.58 (s. 2H). 2.94 (s. 6H). 2.12 (s. 3H).13C NMR (101 MHz. CDCl3) δ 203.3.132.7.111.0. 69.8.54.9.40.0. 29.4. 26.8. IR (cm-1): 969 (w).2913 (w). 2805 (w). 1705 (m). 1588 (vs). 1519 (s). 1353 (m). 1229 (m). 1151 (vs). 945 (m). 901 (w). 823 (m). 762 (w). 698 (w). 593 (w). 563 (m). 533 (m). 510 (m). 484 (w). 432 (w). 400 (w). MS (EI): m/z (%) = 91.0 (6.2), 118.0 (14.88), 133.1 (4.12), 134.1 (100), 135.1 (10.75), 177.1 (12.1, [M+]). L1-Pd(dba): 32.8 mg (0.058 mmol) of L1 and 39.2 mg (0.058 mmol Pd, 15.6 m% Pd) were suspended in 0.5 ml THF in a J. Young NMR tube. A dark red solution formed that was shaken for 1h. Single crystals of L1-Pd(dba) of pentane into a concentrated solution in THF. THF): δ = 67.1 (d, 2JPP = 120.4 Hz, P+Pip3), 20.0 (d, . 25 mg (0.049 mmol) of L2 and 33.5 mg (0.049 mmol Pd, 15.6 m% Pd) were suspended in 0.5 ml THF in a J. Young NMR tube. A dark red solution formed that was shaken for 1h. L2-Pd(dba) was obtained with 0.5 eq. dba as an orange solid. 7.74 (d, J = 15.98 Hz, 3H), 7.70 – 7.65 (m, 5H), 7.40 – 7.35 (m, 9H), 7.22 (d, J = 16.01 Hz, 4H), 3.06 (d, J = 12.91 Hz, 12H), 1.88 – 1.69 (m, 11), 1.69 – 1.59 (m, 8H), 1.54 – 1.39 (m, 12H), 1.39 – 0.99 (m, 11H). 31P NMR (162 MHz, THF): δ = 75.6 (d, 2JPP = 120.8 Hz, P+Pip3), 22.2 (d, 2JPP = 121.2 Hz, PCy2). L1-Pd(oTol)Br: 32.8 mg (0.058 mmol) of L1 and 39.2 mg (0.058 mmol Pd, 15.6 m% Pd) were suspended in 0.5 ml THF in a J. Young NMR tube. A dark red solution formed that was shaken for 1h. Afterwards, 0.1 ml (0.863 mmol, 15 eq.) 4-Bromotoluluene were added and the mixture was shaken overnight. Single crystals of L1-Pd(oTol)Br were obtained by diffusion of Pentane into a con- centrated solution in THF. 31P NMR (162 MHz, THF): δ = 71.4 (d, 2JPP = 103.8 Hz, P+Pip3), 12.5 (d, 2JPP = 103.2 Hz, PCy2). L3-Pd(oTol)Br: 30.0 mg (0.032 mmol) of L3 and 41.8 mg (0.062 mmol Pd, 15.6 m% Pd) were suspended in 0.5 ml THF in a J. Young NMR tube. A dark red solution formed that was shaken for 1h. Afterwards, 0.15 ml (1.23 mmol, 20 eq.) 4-Bromotoluluene were added and the mixture was shaken overnight. Single crystals of L3-Pd(oTol)Br were obtained by diffusion of Pentane into a con- centrated solution in THF. 31P NMR (162 MHz, THF): δ = 72.6 (d, 2JPP = 64.4 Hz, P+Pip3), 25.6 (d, 2JPP = 64.4 Hz, PCy2). 30.0 mg (0.032 mmol) of L3 and 41.8 mg (0.062 mmol Pd, 15.6 m% Pd) were suspended in 0.5 ml THF in a J. Young NMR tube. A dark red solution formed that was shaken for 1h. Afterwards, 0.15 ml (1.23 mmol, 20 eq.) 4-Chlorotoluluene were added and the mixture was shaken overnight. Single crystals of L3-Pd(oTol)Cl were obtained by diffusion of Pentane into a con- centrated solution in THF. 31P NMR (162 MHz, THF): δ = 72.6 (d, 2JPP = 64.4 Hz, P+Pip3), 25.6 (d, 2JPP = 64.4 Hz, PCy2). Isomere: 71.4 (d, 2JPP = 86.7 Hz, P+Pip3), 25.0 (d, 2JPP = 87.2 Hz, PCy2). L2-PdCl2: 25.0 mg (0.049 mmol) of L2 and 12.8 mg (0.049 mmol, 1 eq.) Pd(MeCN)2Cl2 were suspended in 0.5 ml THF in a J. 30 Young NMR tube. Quickly a red solution formed that was shaken for 1h during which L2-PdCl2 precipitated as an orange solid. 31P NMR (162 MHz, THF): δ = 51.4 (d, 2JPP = 15.3 Hz, P+Pip3), 44.7 (d, 2JPP = 15.1 Hz, PCy2). L3-PdCl2: 20.0 mg (0.041 mmol) of L3 and 10.7 mg (0.041 mmol, 1 eq.) Pd(MeCN)2Cl2 were suspended in 0.5 ml THF in a J. Young NMR tube. Quickly a red solution formed that was shaken for 1h dur- ing which L2-PdCl2 precipitated as an orange solid. 31P NMR (162 MHz, THF): δ = 85.3 (d, 2JPP = 58.0 Hz, P+Pip3), 47.5 (d, 2JPP = 58.0 Hz, PCy2). L7-PdCl2: 25.0 mg (0.043 mmol) of L7 and 11.1 mg (0.043 mmol, 1 eq.) Pd(MeCN)2Cl2 were suspended in 0.5 ml THF in a J. Young NMR tube. Quickly a red solution formed that was shaken for 1h during which L7-PdCl2 precipitated as an orange solid. 31P NMR (162 MHz, THF): δ = 85.3 (d, 2JPP = 58.1 Hz, P+), 47.5 (d, 2JPP = 58.0 Hz, PCy2). L1-AuCl: 93.3 mg (0.164 mmol) of L1 and 50.0 mg of Au(tht)Cl (0.164 mmol) were suspended in 4 ml Pentane and stirred overnight. A colorless suspension formed and the solid was filtered off, washed with 3x3 ml Pentane and dried in vacuo. L1-AuCl was obtained as a colorless solid in 88 % yield (110 mg, 0.137 mmol). 7.29 – 7.23 (m, 2H, Phorto), 7.22 – 7.17 (m, 2H, Phmeta), 7.11 – 7.05 (m, 1H, Phpara), 3.02 (q, 3JHP = 5.0 Hz, 12H, Pip Pos.1 CH2), 2.56 – 2.46 (m, 2H, Cy Pos.3, CH2), 1.98 – 1.76 (m, 4H, Cy Pos.1, CH + Cy Pos.2, CH2), 1.66 – 1.52 (m, 4H, Cy Pos.2 + Pos.4, CH2), 1.50 – 1.32 (m, 24H, Pip Pos.2 + Pos.3 CH2; Cy Pos.3, CH2), 1.29 – 1.18 (m, 2H, Cy Pos.4, CH2), 1.17 – 1.05 (m, 4H, Cy Pos.2, CH2). 13C NMR (101 MHz, C6D6): δ = 141.3 (dd, 2JCP = 8.6, 2.6 Hz, Phypso, C), 136.7 (dd, 3JCP = 6.0, 2.4 Hz, Phortho, CH), 127.9 (s, Phmeta, CH), 125.6 (d, 2J = 2.5 Hz, CH), 48.2 (s, Pip Pos.1, CH), 41.0 (dd, 1JCP = 37.9 Hz,3JCP = 3.3 Hz, Cy Pos.1, CH), 33.3 (d, 3JCP = 2.4 Hz, Cy Pos.3, CH2), 31.0 (s, Cy Pos.3, CH2), 29.7 (dd, 1JCP = 196.7, 60.4 Hz, P–C-–P), 28.2 (d, 2JCP = 13.6 Hz, Cy Pos.2, CH2), 27.3 (d, 2JCP = 12.1 Hz, CH2), 26.5 (s, Cy Pos.4, CH2), 26.4 (d, 2JCP = 5.0 Hz, Pip Pos.2, CH2), 25.0 (s, Pip Pos.3, CH2). 31P NMR (162 MHz, C6D6): δ = 54.2 (d, 2JPP = 74.8 Hz, P+Pip3), 31.0 (d, 2JPP = 75.3 Hz, PCy2). L2-AuCl: 83.2 mg (0.164 mmol) of L1 and 50.0 mg of Au(tht)Cl (0.164 mmol) were suspended in 4 ml Pentane and stirred overnight. A colorless suspension formed and the solid was filtered off, washed with 3x3 ml Pentane and dried in vacuo. L2-AuCl was obtained as a colorless solid in 86 % yield (99 mg, 0.134 mmol). 1H NMR (400 MHz, C6D6): δ = 3.09 (q, 3JHP = 5.4 Hz, 12H, Pip Pos.1, CH2), 2.06 – 1.91 (m, 6H, Cy Pos. 1 , CH, + Cy Pos.3, CH2), 1.83 – 1.70 (m, 4H, Cy Pos.2 + Pos.3 , CH2), 1.68 – 1.57 (m, 6H, Cy Pos.3 + Pos.4, CH2), 1.54 (dd, 3JHP = 14.4, 9.9 Hz, 3H, CH3), 1.50 – 1.42 (m, 6H, Pip Pos.3, CH2), 1.39 – 1.29 (m, 12H, Pip Pos.2, CH2), 1.27 – 1.07 (m, 6H, Cy Pos.2 + Pos.3, CH2). 13C NMR (101 MHz, C6D6): δ = 48.0 (s, Pip Pos.1, CH2, 37.8 (dd, 1JCP = 39.2 Hz, 3JCP = 4.3 Hz, Cy Pos.1, CH ), 31.7 (d, 3JCP = 3.9 Hz, Cy Pos.3 , CH2), 30.9 (s, Cy Pos.3, CH2), 27.7 (d, 2JCP = 11.7 Hz, Cy Pos.2, CH2), 27.3 (d, 2JCP = 14.0 Hz, Cy Pos.2, CH2), 26.7 (s, Pip Pos.2, CH2), 26.7 (s, Cy Pos.4, CH2), 25.0 (s, Pip Pos.3, CH2), 16.4 (dd, 3JCP = 6.1, 1.8 Hz, CH3), 7.2 (dd, 1JCP = 196.9, 71.0 Hz, P–C-–P).31P NMR (162 MHz, C6D6): δ = 62.4 (d, 2JPP = 83.0 Hz, P+Pip3), 35.9 (d, 2JPP = 83.1 Hz, PCy2). L5-AuCl: 87.8 mg (0.164 mmol) of L1 and 50.0 mg of Au(tht)Cl (0.164 mmol) were suspended in 4 ml Pentane and stirred overnight. A colorless suspension formed and the solid was filtered off, washed with 3x3 ml Pentane and dried in vacuo. L5-AuCl was obtained as a colorless solid in 54 % yield (65 mg, 0.085 mmol). 1H NMR (400 MHz, C6D6): δ = 3.05 (q, 3J = 5.3 Hz, 12H, Pip Pos.1, CH2), 2.52 – 2.33 (m, 3H, iPr, CH, Cy Pos.3, CH2), 2.11 – 1.98 (m, 4H, Cy Pos.1, CH, Cy Pos.3, CH2), 1.85 – 1.69 (m, 4H, Cy Pos.2, CH2), 1.66 – 1.54 (m, 4H, Cy Pos.2 + Pos.3, CH2), 1.51 – 1.31 (m, 20H, Pip Pos. 2 + Pos.3 + Cy Pos.3, CH2), 1.29 – 1.08 (m, 12H, iPr CH3, Cy Pos.2 + Pos.4, CH2). 13C NMR (101 MHz, C6D6): δ = 48.6 (s, Pip Pos.1, CH2), 41.8 (d, 1JCP = 35.6 Hz, Cy Pos.1, CH), 34.7 (s, Cy Pos.3, CH2) , 32.6 (s, Cy Pos.3, CH2, 30.5 (d, 2JCP = 11.4 Hz, iPr CH(CH3)2, 28.3 (d, 2JCP = 13.7 Hz, Cy Pos.2, CH2), 27.9 (d, 2JCP = 12.2 Hz, Cy Pos.2, CH2), 26.8 (d, 3JCP = 4.8 Hz, iPr, CH(CH3)2), 26.6 (d, 3J = 1.6 Hz, Cy Pos.4, CH2), 26.5 (d, 3JCP = 4.6 Hz, Pip Pos.2, CH2), 25.1 (s, Pip Pos.3). 31P NMR (162 MHz, C6D6): δ = 61.5 (d, 2JPP = 82.1 Hz, P+Pip3), 39.3 – 38.5 (d br, 2JPP = 82.1 Hz, PCy2). L6-AuCl: 74.6 mg (0.164 mmol) of L1 and 50.0 mg of Au(tht)Cl (0.164 mmol) were suspended in 4 ml Pentane and stirred overnight. A colorless suspension formed and the solid was filtered off, washed with 3x3 ml Pentane and dried in vacuo. L6-AuCl was obtained as a colorless solid in 81 % yield (87 mg, 0.085 mmol). 3.11 (q, 3J = 5.8 Hz, 12H, Pip Pos.1, CH2), 1.60 (dd, 3JHP = 14.8, 9.5 Hz, 3H CH3), 1.51 (m, 6H, Pip Pos.3 CH2), 1.35 (d, 3JHP = 14.1 Hz, 18H, tBu, CH3), 1.31 – 1.23 (m, 12H, Pip Pos.2 CH2). 13C NMR (101 MHz, C6D6): δ = 47.8 (s, Pip Pos.1, CH2), 40.9 (dd, 1JCP = 31.7 Hz, 3JCP = 5.7 Hz, tBu C(CH3)3), 31.9 (d, 2JCP = 5.9 Hz, tBu C(CH3)3), 26.9 (d, 3JCP = 4.4 Hz, Pip Pos.2, CH2), 24.9 (s, Pip Pos.3, CH2), 18.4 (dd, 2JCP = 4.9, 2.0 Hz, CH3), 12.4 (dd, 1JCP = 197.3, 70.8 Hz, P–C-–P). 31P NMR (162 MHz, C6D6): δ = 60.7 (d, 2JPP = 87.1 Hz, P+Pip3), 58.3 (d, 2JPP = 87.1 Hz, PCy2). L3-AuCl: 79.7 mg (0.164 mmol) of L3 and 50.0 mg of Au(tht)Cl (0.164 mmol) were suspended in 4 ml Pentane and stirred overnight. A colorless suspension formed and the solid was filtered off, washed with 3x3 ml Pentane and dried in vacuo. L3-AuCl was obtained as a colorless solid in 71 % yield (80 mg, 0.111 mmol) NMR (400 MHz, C6D6): δ = 7.21 – 7.16 (m, 2H, Phortho, CH2), 7.13 – 7.06 (m, 2H, Phmeta, CH2), 7.05 – 6.98 (m, 1H, Phpara, CH2), 3.85 (s, 2H, N(CH2)2N), 2.68 (dq, 3J = 8.6, 5.3 Hz, 2H, N(CH2)2N), 2.42 (d, 3JHP = 9.2 Hz, 6H, NCH3), 2.01 (s, 3H, PCy Pos.1, CH + PCy2 Pos.3, CH2), 1.91 – 1.80 (m, 2H, PCy2 Pos.1, CH), 1.74 (d, 3J = 12.7 Hz, 2H, PCy2 Pos.3, CH2), 1.69 – 1.61 (m, 4H, PCy Pos.2 + PCy2 Pos.2, CH2), 1.59 – 1.48 (m, 4H, PCy Pos.4 + PCy2 Pos.3, CH2), 1.46 – 1.33 (m, 3H, PCy2 Pos.4 + Pos.2, CH2), 1.32 – 1.18 (m, 4H, PCy2 Pos.2, CH2), 1.15 – 1.00 (m, 7H, PCy2 Pos.2 + Pos.3, CH2), 0.84 – 0.55 (m, 4H, PCy2 Pos.2 + Pos.4, CH2). 13C NMR (101 MHz, C6D6): δ = 140.5 (dd, 2JCP = 14.0, 2.9 Hz, Phypso, C), 136.2 (s, Phortho, CH), 127.8 (s, Phmeta, CH), 125.6 (s, Phpara, CH), 47.3 (d, 2J = 6.8 Hz, N(CH2)2N), 39.2 (dd, 1JPCP = 85.1 Hz, 3JCP = 5.4 Hz, PCy Pos.1, CH), 37.5 (d, 1JCP = 38.7 Hz, PCy2, CH), 32.9 (d, 2JCP = 7.0 Hz, N(CH3)), 30.4 (d, 3JCP = 2.4 Hz, PCy2 Pos.3, CH2), 29.9 (s, PCy2 Pos.3, CH2), 28.2 (dd, 1JCP = 114.4, 90.4 Hz, P–C-–P), 27.2 (d, 2JCP = 12.1 Hz, PCy Pos.2, CH2), 26.8 (d, 2JCP = 13.6 Hz, PCy2 Pos.2, CH2), 26.5 (d, 2JCP = 13.6 Hz, PCy2 Pos.3, CH2), 26.2 (s, PCy Pos.3, CH2), 25.9 (s, PCy2 Pos.4, CH2), 22.4 (s, PCy Pos.4, CH2). 31P NMR (162 MHz, C6D6): δ = 61.3 (d, 2JPP = 53.1 Hz, P+), 26.3 (d, 2JPP = 52.5 Hz, PCy2). L10-AuCl: NMR (101 MHz, CD2Cl2): δ = 141.8 (dd, 2JCP = 5.6, 3.3 Hz, oTolipso), 139.4 (dd, 3JCP = 4.9, 2.2 Hz, oTolortho), 139.1 (dd, 3JCP = 12.9, 3.0 Hz, oTolortho’), 131.4 (t, 4JCP = 2.0 Hz, oTolmeta), 126.9 (t, 4JCP = 2.4 Hz, oTolmeta’), 125.9 (t, 5JCP = 2.2 Hz, oTolpara), 48.3 – 48.0 (m, NC2H4N), 41.5 (dd, 1JCP = 85.7 Hz, 3JCP = 5.8 Hz, Cy, C1), 40.4 (dd, 1JCP = 38.7 Hz, 3JCP = 5.2 Hz, PCy2, C1), 37.24 (dd, 1JCP = 37.4 Hz, 3JCP = 1.6 Hz, PCy2, C1), 34.6 (d, 2JCP = 7.0 Hz; NCH3), 34.0 (d, 2JCP = 6.6 Hz, NCH3), 32.4 (d, 2JCP = 2.6 Hz, Cy, C2), 31.7 (s, Cy, C2), 30.8 (d, 3JCP = 1.8 Hz, Cy, C3), 28.7 (d, 3JCP = 4.2 Hz, PCy2, C3), 27.9 (dd, 2JCP = 12.9 Hz, 4JCP = 9.5 Hz, PCy2, C2), 27.5 (dd, 2JCP = 13.1 Hz, 2JCP = 4.8 Hz, PCy2, C2), 27.3 – 27.1 (m, PCy2, C3), 26.8 – 26.7 (m, PCy2, C4), 26.5 (d, 4JCP = 1.6 Hz, Cy, C4), 22.6 (s, CH3, oTol) ppm. The PCP signal could not be observed. 31P{1H} NMR (162 MHz, CD2Cl2): δ = 59.2 (d, 2JPP = 54.1 Hz, PCy(MeNC2H4NMe)), 31.0 (d, 2JPP = 54.1 Hz, PCy2) ppm. IR (ATR): 2919 (m) 2848 (m), 1444 (m), 1219 ((m), 1176 (m), 1020 (s), 950 (s), 922 (m), 729 (m), 548 (m), 484 (m) cm-1. Melting point: 192 °C (decomposi- tion). Elemental analysis for C30H50AuClN2P2: calculated: C 49.15; H 6.87; N 3.82, found: C 48.80; H 6.87; N 3.78. L11-AuCl: (101 MHz, CD2Cl2): δ = 142.5 (dd, 2JCP = 7.1, 3.1 Hz, oTolipso), 139.4 – 139.3 (m, oTolortho), 139.2 (d, 3JCP = 3.2 Hz, oTolortho’), 131.5 (t, 4JCP = 1.8 Hz, oTolmeta), 126.9 (t, 4JCP = 2.3 Hz, oTolmeta’), 126.0 (t, 5JCP = 2.2 Hz, oTolpara), 44.2 (dd, 2JCP = 24.9 Hz, 2JCP = 8.4 Hz, NCH(CH3)2), 43.1 (dd, 1JCP = 82.6 Hz, 3JCP = 5.9 Hz, Cy, C1), 41.1 – 40.4 (m, PCy2, C1), 37.5 (dd, 2JCP = 19.1 Hz, 4JCP = 8.0 Hz, NC2H4N), 34.6 (dd, 2JCP = 73.1 Hz, 4JCP = 3.8 Hz, Cy, C2), 30.7 (s, Cy/PCy2), 29.8 (d, JCP = 1.9 Hz, Cy/PCy2), 28.2 (d, JCP = 12.4 Hz, Cy/PCy2), 28.1 (d, JCP = 8.9 Hz, Cy/PCy2), 27.9 (d, JCP = 6.1 Hz, Cy/PCy2), 27.7 (Cy/PCy2), 27.6 (d, JCP = 14.3 Hz, Cy/PCy2), 27.4 – 27.3 (m, Cy/PCy2), 27.2 (Cy/PCy2), 26.8 (dd, JCP = 4.6, 1.7 Hz, Cy/PCy2), 26.7 (d, JCP = 1.6 Hz), 26.6 (d, JCP = 3.9 Hz), 23.2 (dd, 3JCP = 4.3, 1.6 Hz, CH3, iPr+iPr’), 22.4 (s, CH3, oTol), 21.6 (d, 3JCP = 1.8 Hz, CH3, iPr), 21.4 (d, 3JCP = 2.3 Hz, CH3, iPr’) ppm. The PCP signal could not be observed. 31P{1H} NMR (162 MHz, CD2Cl2): δ = 58.9 (d, 2JPP = 57.0Hz, PCy(iPrNC2H4NiPr)), 29.8 (d, 2JPP = 57.0 Hz, PCy2) ppm. IR (ATR): 2925 (m), 2848 (m), 1444 (w), 1175 (s), 1102 (m), 1065 (s), 1018 (s), 994 (m), 970 (m), 917 (m), 886 (m), 728 (m), 548 (m), 529 (m), 473 (s), 441 (m) cm-1. Melting point: 250 °C (decomposi- tion). Elemental analysis for C34H58AuClN2P2: calculated: C 51.74; H 7.41; N 3.55, found: C 52.08; H 7.58; N 3.55. L12-AuCl: The synthesis of L12AuCl was performed according to the general procedure. Colorless crystals suitable single crys- tal X-ray diffraction experiments were obtained by slow vapor diffusion of pentane into a saturated DCM solution of the compound. Yield: (92.0 mg, 0.109 mmol, 70%). 7.28 (d, 3JHH = 7.5 Hz, 1H, oTolortho), 7.21 (d, 3JHH = 7.3 Hz, 1H, oTolmeta), 7.13 – 7.03 (m, 2H, oTolmeta’+para), 3.66 – 3.53 (m, 2H, NC2H4N), 3.33 – 3.16 (m, 2H, NCH2), 3.16 – 2.98 (m, 4H, NCH2+NC2H4N), 2.56 (s, 3H, CH3, oTol), 2.44 – 2.33 (m, 1H, Cy/PCy2), 2.26 – 2.16 (m, 1H, Cy/PCy2), 1.96 – 1.03 (m, 34H, Cy/PCy2), 0.96 (dd, 3JHH = 6.6, 4.2 Hz, 12H, CH3, iPen), 0.92 – 0.59 (m, 3H, Cy/PCy2) ppm. 142.0 (dd, 2JCP = 5.8, 3.2 Hz, oTolipso), 139.2 (d, 3JCP = 3.0 Hz, oTolortho), 139.1 (d, 3JCP = 3.0 Hz, oTolortho’), 131.5 (d, 4JCP = 1.9 Hz, oTolmeta), 126.9 (d, 4JCP = 2.8 Hz, oTolmeta’), 126.1 (s, oTol- para), 46.4 (t, J = 6.1 Hz, NCH2), 45.5 (dd, 2JCP = 18.7 Hz, 4JCP = 6.8 Hz, NC2H4N), 41.9 (dd, 1JCP = 41.9 Hz, 3JCP = 5.4 Hz, Cy, C1), 41.3 (t, J = 5.5 Hz, PCy2, C1), 38.7 – 38.2 (m, CH2, iPen+PCy2, C1), 33.7 (dd, JCP = 6.4, 3.1 Hz, Cy/PCy2), 30.6 (d, 2JCP = 21.2 Hz, Cy, C2), 28.22 – 26.62 (m, Cy/PCy2), 23.2 (d, 5JCP = 4.1 Hz, CH3, iPen), 22.8 (d, 5JCP = 7.2 Hz, CH3, iPen), 22.4 (s, CH3, oTol) ppm. The PCP signal could not be observed. 31P{1H} NMR (162 MHz, CD2Cl2): δ = 60.9 (d, 2JPP = 55.8 Hz, PCy(iPenNC2H4NiPen)), 31.3 (d, 2JPP = 55.8 Hz, PCy2) ppm. IR (ATR): 2923 (s), 2848 (m), 1444 (m), 1156 (s), 1113 (m), 1067 (s), 1023 (s), 996 (m), 921 (m), 888 (w), 754 (m), 729 (s), 545 (m), 515 (m), 471 (s) cm-1. Melting point: 191 °C (decomposition). Elemental analysis for C38H66AuClN2P2: calculated: C 53.99; H 7.87; N 3.31, found: C 53.68; H 8.11; N 3.25 L13-AuCl: The synthesis of L13AuCl was performed according to the general procedure. Colorless crystals suitable for single crys- tal X-ray diffraction experiments were obtained by slow va- por diffusion of pentane into a saturated benzene solution of the compound. Yield: (89.0 mg, 0.116 mmol, 74%). 1H NMR and 13C{1H} NMR could not be evaluated due to the presence of two different conformers in solution. Complex decomposition is observed during high temperature NMR spectroscopy. 31P{1H} NMR (162 MHz, CD2Cl2): δ = 81.0 (d, 2JPP = 75.6 Hz, PCy(neoPenNC2H4NneoPen)), 78.1 (d, 2JPP = 50.0 Hz, PCy(neoPenNC2H4NneoPen)), 36.9 (d, 2JPP = 75.6 Hz, PCy2), 34.8 (d, 2JPP = 50.0 Hz, PCy2). IR (ATR): 2924 (s), 2847 (m), 1443 (w), 1181 (w), 1162 (w), 1138 (w), 1108 (w), 1065 (s), 1034 (m), 1034 (m), 985 (w), 926 (s), 883 (m), 850 (w), 736 (m), 604 (w), 570 (s), 520 (m), 502 (m), 426 (m) cm-1. Melting point: 210 °C (decomposition). Elemental analysis for C32H62AuClN2P2: calculated: C 49.97; H 8.12; N 3.64, found: C 49.77; H 8.14; N 3.55. L14-AuCl: The synthesis of L14AuCl was performed according to the gen- eral procedure. Colorless crystals suitable for single crystal X- ray diffraction experiments were obtained by slow vapor diffu- 5 sion of pentane into a saturated DCM solution of the compound. Yield: (76.0 mg, 0.097 mmol, 62%). 6.86 (d, 5JHP = 2.5 Hz, 4H, Mesmeta), 4.29 – 4.16 (m, 1H, Cy, H1), 3.7 (s, 2H, NC2H4N), 3.6 (s, 2H, NC2H4N’), 2.50 (d, 5JHP = 3.9 Hz, 12H, CH3, Mesortho), 2.22 (s, 8H, CH3, Mespara+Cy, H2), 2.08 – 1.93 (m, 2H, CH(CH3)2), 1.79 – 1.58 (m, 4H, Cy, H3+4), 1.43 (dd, 3JHP = 14.8, 10.6 Hz, 3H, PCPCH3), 1.37 – 1.13 (m, 4H, Cy, H2+3), 1.07 (dd, 3JHP = 16.9, 3JHH = 7.0 Hz, 6H, CH3, iPr), 0.75 (dd, 3JHP = 16.9, 3JHH = 7.1 Hz, 6H, CH3, iPr’) ppm. 139.2 (d, 2JCP = 5.0 Hz, Mesipso), 137.3 (s, Mesortho), 137.0 (s, Mesortho’), 136.2 (d, 5JCP = 1.3 Hz, Mespara), 131.2 (s, Mesmeta), 131.0 (s, Mesmeta’), 51.0 (d, 2JCP = 8.8 Hz, NC2H4N), 40.8 (dd, 1JCP = 85.4 Hz, 3JCP = 2.3 Hz, Cy, C1), 29.4 (s, Cy, C2+ CH(CH3)2), 26.8 (d, 4JCP = 1.9 Hz, Cy, C4), 26.4 (d, 3JCP = 14.7 Hz, Cy, C3), 21.6 (s, CH3, Mesortho), 20.9 – 20.8 (m, CH3, iPr), 20.8 (s, CH3, Mespara), 17.6 (dd, 1JCP = 141.8, 64.3 Hz, PCP), 15.7 (d, 2JCP = 1.7 Hz, PCPCH3) ppm. 31P{1H} NMR (162 MHz, CD2Cl2): δ = 58.1 (d, 2JPP = 74.1 Hz, PiPr2), 47.9 (d, 2JPP = 74.1 Hz, PCy(MesNC2H4NMes)). IR (ATR): 2925 (w), 1475 (m), 1245 (s), 1187 (w), 1149 (m), 1060 (s), 914 (s), 851 (m), 823 (s), 739 (m), 654 (m), 625 (m), 601 (m), 562 (s), 510 (m), 444 (w), 416 (w) cm-1. Melt- ing point: 237 °C (decomposition). Elemental analysis for C34H54AuClN2P2: calculated: C 52.01; H 6.93; N 3.57, found: C 51.71; H 7.02; N 3.32. L15-AuCl: The synthesis of L15AuCl was performed according to the general procedure. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow vapor diffusion of pentane into a saturated DCM solution of the compound. Yield: (108 mg, 0.137 mmol, 88%). 1H NMR and 13C{1H} NMR could not be evaluated due to the presence of two different conformers in solution. Complex decomposition is observed dur- ing high temperature NMR spectroscopy. 31P{1H} NMR (162 MHz, CD2Cl2): δ = 60.8 (d, 2JPP = 53.2 Hz), 59.6 (d, 2JPP = 51.2 Hz), 31.9 (d, 2JPP = 53.2 Hz, PCy2), 31.2 (d, 2JPP = 51.2 Hz, PCy2) ppm. IR (ATR): 293 (m), 2848 (m), 1442 (w), 1212 (m), 1178 (m), 1012 (s), 922 (m), 890 (m), 847 (w), 807 (w), 759 (w), 730 (m), 552 (m), 523 (m), 482 (m), 424 (m) cm-1. Melting point: 223 °C (decomposition). Elemental analysis for C34H56AuClN2P2: cal- culated: C 51.88; H 7.17; N 3.56, found: C 51.85; H 7.12; N 3.51. L16-AuCl: The phosphine L16 (96.6 mg, 0.172 mmol) and (tetrahy- drothiophene)gold(I) chloride (50.0 mg, 0.156 mmol) were dissolved in toluene (5 ml) and stirred over night at room temperature. The solution was overlaid with pentane (15 ml) and left overnight. A colorless solid precipitated from the solution. The solid was filtered off and washed with pentane (3 x 5 ml). The gold complex L7AuCl was obtained as a colorless solid after drying at 50 °C in vacuo. Col- orless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow vapor diffusion of pentane into a saturated DCM solution of the compound. Yield: (85.0 mg, 0.103 mmol, 66%). 7.27 – 7.20 (m, 2H, oTolortho+para), 7.16 (t, 3JHH = 7.4 Hz, 1H, oTolmeta), 7.08 (t, 3JHH = 7.4 Hz, 1H, oTolmeta’), 3.82 (brs, 8H, Mor), 3.38 (brs, 12H Mor), 2.63 – 2.29 (m, 9H, CH3, oTol+PCy2, H3+Mor), 1.94 – 0.98 (m, 20H, PCy2) ppm. NMR (101 MHz, CD2Cl2): δ = 143.1 (dd, 2JCP = 7.1, 2.6 Hz, oTolipso), 139.3 (dd, 3JCP = 4.7, 2.0 Hz, oTolortho), 138.1 (dd, 3JCP = 7.7, 2.9 Hz, oTolortho’), 131.45 (t, JCP = 1.7 Hz, oTolpara), 127.4 (t, JCP = 2.5 Hz, oTolmeta), 125.8 (q, JCP = 2.5 Hz, oTolmeta’), 67.2 (s, Mor, C2), 48.1 (s, Mor, C3), 41.5 (dd, 1JCP = 37.6 Hz, 3JCP = 2.1 Hz, PCy2, C1), 40.9 (dd, 1JCP = 37.6 Hz, 3JCP = 5.7 Hz, PCy2, C1), 35.3 (d, 3JCP = 3.3 Hz, PCy2, C3), 34.4 (d, 3JCP = 2.7 Hz, PCy2, C3), 30.9 (s, PCy2, C3), 30.1 (d, 3JCP = 1.7 Hz, PCy2, C3), 28.4 (d, 2JCP = 14.0 Hz, PCy2, C2), 28.0 (d, 2JCP = 14.1 Hz, PCy2, C2), 27.6 (dd, JCP = 11.8, 8.9 Hz, PCy2, C2), 26.7 – 26.5 (m, PCy2, C4), 22.4 (s, CH3, oTol) ppm. The PCP signal could not be observed. 31P{1H} NMR (162 MHz, CD2Cl2): δ = 50.2 (d, 2JPP = 76.2 Hz, P(Mor)3), 34.0 (d, 2JPP = 76.2 Hz, PCy2) ppm. IR (ATR): 2918 (w), 2847 (w), 1444 (w), 1251 (m), 1107 (s), 1081 (m), 1020 (m), 997 (w), 950 (s), 917 (m), 846 (w), 732 (m), 707 (m), 589 (w), 497 (m), 473 (m) cm-1. Melting point: 246 °C (decomposition). Elemental analysis for C32H53AuClN3O3P2: calcu- lated: C 46.75; H 6.50; N 5.11, found: C 46.45; H 6.38; N 4.98. L17-AuCl: The synthesis of L17AuCl was performed according to the general procedure. Colorless crystals suitable for single crystal X-ray diffraction experiments were obtained by slow vapor diffusion of pentane into a saturated DCM solution of the compound. Yield: (92.0 mg, 0.114 mmol, 73%). NMR (101 MHz, CD2Cl2): δ = 146.9 (d, 2JCP = 3.6 Hz, Phipso), 129.5 (s, Phmeta), 127.8 (d, 3JCP = 2.9 Hz, Phortho), 126.0 (s, Phpara), 42.3 (d, 2JCP = 3.9 Hz, CH3NPh), 37.6 (dd, 1JCP = 39.1 Hz, 3JCP = 4.6 Hz, PCy2, C1), 31.8 (d, 3JCP = 2.7 Hz, PCy2, C3), 31.4 (s, PCy2, C3), 27.9 (d, 2JCP = 12.5 Hz, PCy2, C2), 27.5 (d, 2JCP = 13.6 Hz, PCy2, C2), 26.6 (d, 4JCP = 1.6 Hz,), 16.5 (d, 2JCP = 8.0 Hz, PCPCH3), 13.8 (dd, 1JCP = 213.4, 68.8 Hz, PCP) ppm. 31P{1H} NMR (162 MHz, CD2Cl2): δ = 51.9 (d, 2JPP = 82.2 Hz, P(PhNMe)3), 38.2 (d, 2JPP = 82.2 Hz, PCy2) ppm. IR (ATR): 2927 (w), 1490 (m), 1447 (w), 1261 (w), 1183 (m), 1058 (m), 1023 (m), 909 (s), 883 (s), 775 (m), 767 (m), 700 (s), 555 (m), 539 (s), 517 (w), 464 (w) cm-1. Melting point: 208 °C (decomposition). Elemental analysis for C35H49AuClN3P2: calculated: C 52.15; H 6.13; N 5.21, found: C 52.12; H 6.16; N 5.14. L1-Rh(acac)CO: 30.0 mg (0.053 mmol) of L1 and 13.6 mg of Rh(acac)(CO)2 (0.053 mmol) were suspended in 0.5 ml DCM and for 1 h. Single crystals of L1-Rh(acac)CO were obtained by slow diffusion of Pentane into a concentrated solution in DCM. 31P NMR (162 MHz, C6D6): δ = 52.5 (d, 2JPP = 78.9 Hz, P+Pip3), 39.5 (dd, 1JRhP = 163.6 Hz, 2JPP = 78.5.1 Hz, PCy2). L2-Rh(acac)CO: 25.0 mg (0.049 mmol) of L2 and 12.7 mg of Rh(acac)(CO)2 (0.049 mmol) were suspended in 0.5 ml DCM and for 1 h. Single crystals of L2-Rh(acac)CO were obtained by slow diffusion of Pentane into a concentrated solution in DCM. 31P NMR (162 MHz, C6D6): δ = 62.4 (d, 2JPP = 84.1 Hz, P+Pip3), 39.4 (br, PCy2). L3-Rh(acac)CO: 25.0 mg (0.051 mmol) of L3 and 13.3 mg of Rh(acac)(CO)2 (0.051 mmol) were suspended in 0.5 ml DCM and for 1 h. Single crystals of L3-Rh(acac)CO were obtained by slow diffusion of Pentane into a concentrated solution in DCM. MHz, C6D6): δ = 77.8 (dd, 2JPP = 66.2 Hz, 3JRhP = 4.7 Hz, P+Pip3), 39.4 (dd, 2JPP = 66.2 Hz, 1JRhP = 147.2 Hz, PCy2). L1-Rh(CO)2 Cyclometallated: 30.0 mg (0.053 mmol) of L1 and 13.6 mg of Rh(acac)(CO)2 (0.053 mmol) were suspended in 0.5 ml DCM and for 1 h. Single crystals of L1-Rh(CO)2 were ob- tained by slow diffusion of Pentane into a concentrated solution in DCM. 31P NMR (162 MHz, CD2Cl2): δ = 79.6 (dd, 2JPRh = 140.5 Hz, 2JPP = 6.6 Hz, PCy2), 50.9 (dd, 2JPP = 6.7 Hz, 3JRhP = 10.6 CD2Cl2) δ 7.54 (d, J = 7.18 Hzz), 6.71 (t, J = 7.49 Hz, 1H), 6.63 (d, J = 7.97 Hz, 1H), 6.24 (td, J = 7.11, 1.39 Hz, 1H), 3.59 – 2.67 (m, 14H), 2.15 – 1.18 (m, 48H). 13C NMR (101 MHz, CD2Cl2) δ 195.81 – 192.02 (m), 165.52 – 164.97 (m), 145.29 (d, J = 3.82 Hz), 124.56, 120.02 (d, J = 21.75 Hz), 115.92, 48.04, 38.91 (d, J = 26.31 Hz), 32.70 (d, J = 2.93 Hz), 30.40 (d, J = 4.40 Hz), 27.21 (dd, J = 42.63, 12.51 Hz), 26.24 (d, J = 4.12 Hz), 24.67. ml and dried in vacuo. 83.6 mg (0.194 mmol, 49.1 %) of the complex were obtained as an orange solid. Single crystals of L2-Ni(benzaldehyde) were obtained by slow diffusion of Pentane into a concentrated solution in THF. 31P NMR (162 MHz, THF): δ = 72.2 (d, 2JPP = 116.2 Hz, PCy2), 26.8 (dd, 2JPP = 116.2 Hz, P+Pip3). Monoarylation of acetone Ligand Base Base conc. Pd eq. [M] Source Yield Monoarylation of ammonia Ligand Yield mono Yield di [%] Ratio [%] [Mono:di] 21 32 0,65 68 12 5,5

Claims

Claims 1. A ligand of formula 1, Formula 1 wherein R1 is alkyl, perfluoroalkyl, aryl or cycloalkyl, each unsubsti- tuted or substituted, cyano, sulfonyl -SO2-R10 with R10= C1-C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each unsubstituted or substituted with C1-C4 alkyl or C1-C4 perfluoroalkyl; silyl -Si(R20R30R40) with R20, R30 and R40, independently from each other being C1-C6-alkyl or C5- C10 aryl, each unsubstituted or substituted with C1-C4 alkyl; R2 is alkyl, cycloalkyl, adamantyl or aryl, each substituted or unsubsti- tuted; R3, R4 and R5 is alkyl, cycloalkyl or aryl, which each can be unsubsti- tuted or substituted; or at least two of R3, R4 and R5 are an alkyl or alkylether bridge and together with the phosphorus atom, are forming a heterocyclic ring, or wherein R3 and R6 and/or R4 and R7 and/or R5 and R8 are together forming an alkyl or alkylether bridge, taken together with the nitrogen atom they are connected to, are forming a heterocyclic ring; R6, R7 and R8 are alkyl or aryl, which can be unsubstituted or substi- tuted or, individually or collectively are forming a heterocyclic ring with R3, R4 or R5 and the nitrogen atom they are connected to; m, n and o are 0 or 1, with the proviso that at least one of m, n and o is 1.
2. A ligand of claim 1, wherein R1 is selected from C1 to C9 alkyl, C4-C8 cycloalkyl, C5-C10 aryl, cyano, sulphonyl -SO2-R10 where R10= C1- C5 alkyl, C5-C6 cycloalkyl, C5-C10 aryl, each unsubstituted or substi- tuted by one or more C1 to C4 alkyl, C1 to C4 alkoxy or C1 to C4 per- fluoroalkyl; silyl -Si(R20R30R40) where R20, R30 and R40, each of which is independently C1-C6 alkyl or C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl, or R1 is C5-C10 aryl which may be substituted one or more times by C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl
3. A ligand of claim 1, wherein R2 is C1 to C9 alkyl, C4-C8 cycloalkyl, ad- amantyl, C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 per- fluoroalkyl.
4. A ligand of claim 1, wherein R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4-C8 cycloalkyl, adamantyl, C5 to C10 aryl, which can be unsubstituted or substituted with C1 to C5 alky, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or at least two of R3, R4 and R5 are a C2 to C10 alkyl, C2 to C10 alkenyl or C2 to C10 alkylether bridge and together with the phosphorus atom, are forming a hetero- cyclic ring.
5. A ligand of claim 1, wherein R3, R4 and R5 are, independently from each other, C1 to C5 alkyl, C4-C8 cycloalkyl, adamantyl, C5 to C6 aryl, which can be unsubstituted or substituted with C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or at least two of R3, R4 and R5 are a C2 to C5 alkyl, C2 to C5 alkenyl or C2 to C4 alkylether bridge and together with the phosphorus atom, are forming a heterocyclic ring.
6. A ligand of claim 1, wherein at least two of R3, R4 and R5 together are a C2 to C8 alkyl or C2 to C8 alkylether bridge, optionally substituted with one or more C1 to C5 alkyl or cycloalkyl groups; or the C2 to C8 alkyl or C2 to C8 alkylether bridge being part of a fused C4 to C8 cy- cloalkyl ring, forming a heterocyclic ring with the phosphorous atom.
7. R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be un- substituted or substituted with one or more C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl; or, individually or collectively are forming a heterocyclic ring with R3, R4 or R5 and the nitrogen atom they are connected to.
8. A ligand of claim 1, wherein R3 and R6 and/or R4 and R7 and/or R5 and R8, taken together are a C2 to C8 alkyl or C2 to C8 alkylether bridge, optionally substituted with one or more C1 to C5 groups or the C2 to C8 alkyl or C2 to C8 alkylether bridge being part of a fused C4 to C8 cycloalkyl ring, taken together with the nitrogen atom they are con- nected to, are forming a heterocyclic ring.
9. A ligand of claim 1, wherein R1 represents C1 to C9 alkyl, C4-C8 cyclo- alkyl, C5-C10 aryl, which aryl can be unsubstituted or substituted with C1 to C5 alkyl, C1 to C5 alkoxy or C1 to C5 perfluoroalkyl.
10. A ligand of claim 1, wherein R1 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert. butyl, n-pentyl, n-pentyl (amyl), 2- pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (iso-pentyl or iso-amyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, trifluoromethyl, cyclobutyl, cyclopentyl, cyclo- hexyl, menthyl, phenyl, o-toluyl, naphthyl, o-methoxyphenyl, o-ethox- yphenyl, di-(o-methoxy)phenyl, p-trifluoromethylphenyl, trimethylsilyl, triisopropyl-silyl, tri-tert. - butylsilyl, cyano, methylsulfonyl, toluyl- sulfonyl and trifluoromethylsulfonyl.
11. A ligand of claim 1, wherein R2 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert. butyl, n-pentyl, n-pentyl (amyl), 2- pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (iso-pentyl or iso-amyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2, 2-dimethylpropyl (neopentyl), n-hexyl, trifluoromethyl, cyclobutyl, cyclopentyl, cyclo- hexyl, 1-adamantyl, 2-adamantyl, phenyl, o-, m-, or p-methylphenyl, naphthyl.
12. A ligand of claim 1, wherein R3, R4, R5, R6, R7 and R8, independently of each other, are selected from methyl, ethyl, propyl, isopropyl, n-bu- tyl, sec-butyl, tert-butyl, n-pentyl butyl, n-pentyl, n-pentyl (amyl), 2- pentyl (sec-pentyl), 3-pentyl, 2-methylbutyl, 3-methylbutyl (iso-pentyl or iso-amyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl (neopentyl), n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, me- sityl.
13. A ligand of claim 1, wherein at least two of m, n and o are 1.
14. A ligand of claim 1, wherein all of m, n and o are 1.
15. A ligand of claim 1, wherein R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl, sulphonyl -SO2-R10 where R10= C5-C10 aryl, which is unsubstituted or substituted by C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl; R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4- C8 cycloalkyl, adamantyl, C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl; and/or wherein R3 and R6 and/or R4 and R7 and/or R5 and R8, taken together are a C2 to C8 alkyl or C2 to C8 alkylether bridge, optionally said C2 to C8 alkyl bridge may be partially or entirely part of a fused C4 to C8 cyclo- alkyl ring.
16. A ligand of claim 1, wherein R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl, sulphonyl -SO2-R10 where R10= C5-C10 aryl, which is unsubstituted or substituted by C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl; At least two of m, n and o are 1; at least two of R3, R4 and R5 together are a C2 to C8 alkyl or C2 to C8 alkylether bridge, optionally substituted with one or more C1 to C5 al- kyl or cycloalkyl groups; or the C2 to C8 alkyl or C2 to C8 alkylether bridge being part of a fused C4 to C8 cycloalkyl ring, forming a hetero- cyclic ring with the phosphorous atom; R6, R7 and/or R8 are C1 to C6 alkyl, or C5-C10 aryl, which is unsubsti- tuted or substituted with one or more C1 to C5 alkyl; with the proviso that if one of R3, R4 and R5 is not a C2 to C8 alkyl bridge or a C2 to C8 alkylether bridge, it is C4-C8 cycloalkyl or ada- mantyl.
17. A ligand of claim 1, wherein R1 is C1 to C9 alkyl, C5-C10 aryl, each unsubstituted or substituted by C1 to C4 alkyl, sulphonyl -SO2-R10 where R10= C5-C10 aryl, which is unsubstituted or substituted by C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl; R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4- C8 cycloalkyl, adamantyl, C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl; and/or wherein R3 and R6 and/or R4 and R7 and/or R5 and R8, taken together are a C2 to C8 alkyl or C2 to C8 alkylether bridge, optionally said C2 to C8 alkyl bridge may be partially or entirely part of a fused C4 to C8 cyclo- alkyl ring.
18. A ligand of claim 1, wherein R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl; m is 0, n and o are 1 R3 is C4-C8 cycloalkyl or adamantyl; R4 and R5 together are a C2 to C8 alkyl or C2 to C8 alkylether bridge forming a heterocyclic ring with the phosphorous atom, said C2 to C8 alkyl or C2 to C8 alkylether bridge optionally substituted with one or more C1 to C5 alkyl groups; or the C2 to C8 alkyl or C2 to C8 al- kylether bridge entirely or partially being part of a fused C4 to C8 cy- cloalkyl ring; R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubsti- tuted or substituted with one or more C1 to C5 alkyl.
19. A ligand of formula 1, wherein R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl; m, n and o are 1; and R3, R4 and R5 are, independently from each other, C1 to C9 alkyl, C4- C8 cycloalkyl or C5 to C10 aryl; R6, R7 and R8 are C1 to C9 alkyl or C5 to C10 aryl, which can be unsubstituted or substituted with one or more C1 to C5 alkyl.
20. A ligand of formula 1, wherein R1 is C1 to C9 alkyl or C5-C10 aryl, each unsubstituted or substituted by one or more C1 to C4 alkyl; R2 is C1 to C9 alkyl, C4-C8 cycloalkyl or adamantyl; m, n and o are 1; and R3 and R6, R4 and R7, R5 and R8, each of the pairs taken together are a C2 to C8 alkyl bridge or C2 to C8 alkylether bridge, optionally said C2 to C8 alkyl bridge may be partially or entirely part of a fused C4 to C8 cycloalkyl ring.
21. A ligand of formula 1, wherein R1 is selected from methyl, isopropyl, phenyl, o-tolyl.
22. A ligand of formula 1, wherein R2 is selected from methyl, isopropyl, tert.-butyl, cyclohexyl, phenyl and adamantyl.
23. A ligand of formula 1, wherein R3, R4 and R5 is methyl, phenyl, me- sityl.
24. A ligand of formula 1, wherein one or more of R6, R7 and R8 is methyl, isopropyl, isopentyl, neopentyl, phenyl, mesityl.
25. A ligand of claim 1, wherein R3 and R6 and/or R4 and R7 and/or R5 and R8, taken together with the nitrogen atom they are connected to, are forming a piperidinyl or morpholinyl ring.
26. A ligand of claim 1, wherein R3 with R6 and R4 with R7 and R5 with R8, taken together with the nitrogen atom they are connected to, are forming a piperidinyl or morpholinyl ring.
27. A metal complex, comprising a transition metal and a ligand of any of claims 1 to 26 and optionally comprising at least one organic ligand L and/or at least one halogen X.
28. A method for carrying out a coupling reaction comprising the steps of - providing a reaction mixture comprising at least a substrate, a cou- pling partner and a metal complex comprising a ligand according to any one of claims 1 to 26; and - reacting the substrate with the coupling partner in the presence of the metal complex or its derivative to form a coupling product.
29. A method of carrying out a coupling reaction according to claim 28, wherein the metal complex comprising a ligand is a metal complex ac- cording to claim 27.
30. The method according to one or more of claims 29 to 30, wherein the coupling reaction can be selected from the group consisting of (i) catalytic hydrofunctionalization reactions of alkynes and alkenes; (ii) catalytic hydroamination reactions of alkynes and alkenes; (iii) catalytic O-H addition reactions on alkynes and alkenes; (iv) catalytic coupling reactions; (v) catalytic Kumada coupling reactions, Murahashi coupling reac- tions, Negishi coupling reactions, or Suzuki coupling reactions, espe- cially for the production of biarylene; (vi) catalytic cross-coupling reactions, in particular C-N and C-O cou- pling reactions; and/or (vii) catalytic Heck coupling reactions, in particular for the prepara- tion of arylated olefins, and Sonogashira coupling reactions, in particu- lar for the preparation of arylated and alkenylated alkynes. (viii) catalytic α-arylations of carbonyl compounds and imines.
EP24703511.6A 2023-02-28 2024-02-02 Mixed p,n-donor ligands, their complexes and use thereof Pending EP4665738A1 (en)

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