KR101120054B1 - Novel coordination complexes and process of producing polycarbonate by copolymerization of carbon dioxide and epoxide using the same as catalyst - Google Patents

Abstract

The present invention is a complex compound capable of an equilibrium structural formula synthesized from a ligand containing an ammonium salt and capable of taking a negative charge of two or more metals, and a method of preparing a polycarbonate by copolymerizing an epoxide compound and carbon dioxide using the catalyst as a catalyst. It is about.

According to the present invention, the catalyst shows high activity and high selectivity in copolymerizing the epoxide compound and carbon dioxide and can provide a high molecular weight polycarbonate, which is easy to apply to commercial processes. In addition, by using the complex as a catalyst, the epoxide and carbon dioxide may be copolymerized to prepare a polycarbonate, and then the catalyst may be separated and recovered from the copolymer.

Complex compound, diedentate, catalyst, copolymerization

Description

Novel coordination complexes and process of producing polycarbonate by copolymerization of carbon dioxide and epoxide using the same as catalyst}

The present invention relates to a novel catalyst useful for the production of polycarbonates from epoxide compounds and carbon dioxide and a process for producing polycarbonates using the same. More specifically, the catalyst used to prepare the polymer is a complex compound having an equilibrium structure where the metal center can take a negative divalent or higher form charge, and the production of polycarbonate by copolymerization of carbon dioxide and epoxide using the catalyst as a catalyst. It is about a method. The present invention also relates to a method for separating and recovering a catalyst from a solution in which a copolymer and a catalyst are dissolved after performing a polymerization reaction using the catalyst.

Aliphatic polycarbonates are biodegradable polymers, for example, useful materials for packaging or coatings. The method of preparing polycarbonate from epoxide compound and carbon dioxide is environmentally friendly in that it does not use toxic compound, phosgene, and can obtain carbon dioxide at low cost.

Since the 1960s, many researchers have developed various types of catalysts for producing polycarbonates from epoxide compounds and carbon dioxide. Recently, the present inventor introduced a complex compound having a metal center having onium salt and Lewis acid group in one molecule as a catalyst of a carbon dioxide / epoxide copolymerization reaction, and the catalyst was introduced into a medium of a polymerization reaction in which the catalyst copolymerized with an epoxide compound and carbon dioxide. The growth point of the polymer chain is always located around the metal regardless of its concentration, so it exhibits high activity even under high monomer / catalyst ratios, and can reduce the amount of catalyst used. In addition, it has been developed a catalyst that can increase the conversion rate and facilitate the removal of the heat of polymerization reaction by implementing the polymerization activity even at high temperature, which is easy to apply the commercial process [Korea Patent Application No. 10-2007-0043417 (Application Date: 2007.05.04, Title of the invention: complexes having two components in one molecule, and Method for producing polycarbonate by copolymerization of carbon dioxide and epoxide using as a catalyst); International Patent Application No. PCT / KR2008 / 002453; Eun Kyung Noh, Sung Jae Na, Sujith S, Sang-Wook Kim, and Bun Yeoul Lee * J. Am . Chem . Soc . 2007 , 129 , 8082-8083 (2007.07.04)]. In addition, when the complex compound having a metal center having onium salt and Lewis acid group in one molecule is used as a catalyst for carbon dioxide / epoxide copolymerization reaction, the catalyst can be easily separated and reused after copolymerization. A method for separating and recovering a catalyst has been published in a patent application and an eminent chemistry journal [Korean Patent Application No. 10-2008-0015454 (filed date Feb. 20, 2008, title of the invention: a method for recovering a catalyst from a copolymer production process). ; Cleavage, Sujith S, Eun-Kyoung Noh, Min-Kee Min, "A process producing polycabonate and a coordination complexes used there for" PCT / KR2008 / 002453 (April 30, 2008); Sujith S, Jae Ki Min, Jong Eon Seong, Sung Jea Na, and Bun Yeoul Lee * "A Highly Active and Recyclable Catalytic System for CO ₂ / (Propylene Oxide) Copolymerization" Angew. Chem . Int . Ed . , 2008 , accepted.]

The complexes synthesized in the present inventors' study are mainly Salen-cobalt compounds ([H ₂ Salen = N , N′- bis (3,), obtained from the Schiff base ligands of salicyaldehyde and diamine compounds. 5-dialkylsalicylidene) -1,2-cyclohexanediamine] (see formula below), a tetradentate (or quadradentate) cobalt compound line in which two nitrogen imine ligands and two phenolate ligands are coordinated to cobalt trivalent simultaneously Is a complex compound.

The complex may be referred to as a techladentate (or quadradentate) easy-base complex, which is prepared according to the following scheme.

The tetradentate (or quadradentate) readily-base cobalt or chromium complexes have been developed in depth as existing carbon dioxide / epoxide copolymerization catalysts. (Cobalt based catalysts: (a) Lu, X.-B .; Shi, L .; Wang, Y.-M .; Zhang, R .; Zhang, Y.-J .; Peng, X.-J .; Zhang, Z.-C .; Li, B. J. Am . Chem . Soc . 2006 , 128 , 1664. (b) Cohen, CT Thomas, CM Peretti, KL Lobkovsky, EB Coates, GW Dalton Trans. 2006 , 237 (c) Paddock, RL Nguyen, ST Macromolecules 2005 , 38, 6251. Chromium-based catalysts: (a) Darensbourg, DJ; Phelps, AL; Gall, NL; Jia, L. Acc . Chem . Res . 2004 , 37, 836. (b) Darensbourg, DJ; Mackiewicz, RM J. Am . Chem . Soc . 2005 , 127 , 14026.).

While the present inventors have studied the properties and structures of the conventional tetradentate (or quadradentate) complex having the above structure, surprisingly, in the complex described above, the activity and selectivity of the complex obtained according to the R group varies greatly. I found flying. That is, in the above complex, when the R group has a steric hindrance such as t-butyl, the activity and selectivity are generally predicted, but when reducing the steric hindrance of the R group, for example, a radical such as methyl It was found that the activity (TOF, turnover frequency) jumped about 20 times from 1300 h ⁻¹ to 26000 h ⁻¹ and increased selectivity from 84% to 99% compared to t-butyl compound. Based on these findings, the inventors conducted structural analysis of ¹ H MNR, ¹³ C MNR, ¹⁵ N MNR, ¹⁹ F NMR, IR, IAP-AES, elemental analysis, electrochemistry, and the like. Likewise, when the steric hindrance is a small radical, it has surprisingly been found that complexes having different structures, ie diedentate complexes, in which adjacent nitrogen is not coordinated to the metal are produced, and the complexes have high activity and selectivity.

Accordingly, the first technical problem of the present invention is to coordinate with monodentate, diedentate, or tridentate ligands that include at least one proton group, rather than the existing tetradentate (or quadradate) complex. It is to provide a carbon dioxide / epoxide copolymerization method using a complex compound.

The second technical problem of the present invention is to provide a method for preparing a copolymer using the complex compound as a catalyst and then separating and recovering the catalyst from the resulting mixture solution of the copolymer and the catalyst.

The third technical problem of the present invention is to provide the new complex compound.

According to an aspect of the present invention, using a complex of the formula (1) as a catalyst, alkylene oxide having 2 to 20 carbon atoms unsubstituted or substituted with halogen or alkoxy; Cycloalkene oxide having 4 to 20 carbon atoms unsubstituted or substituted with halogen or alkoxy; And copolymerizing an epoxide compound selected from the group consisting of styrene oxides having 8 to 20 carbon atoms or unsubstituted or substituted with halogen, alkoxy, or alkyl, and carbon dioxide.

[Formula 1]

Wherein M is a metal element;

L is an L-type or X-type ligand;

a is 1, 2, or 3; When a is 1, L contains two or more proton groups, and when a is 2 or 3, each L may be the same or different from each other and may be connected to each other to form a bidentate or tridentate. Can be chelated to the metal as a ligand, at least one L contains at least one proton, and the total number of protons contained in L is at least 2,

Each X independently represents a halogen anion; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^-; HCO ₃ ^-; An aryloxy anion having 6 to 20 carbon atoms and a carboxy anion having 1 to 20 carbon atoms, with or without a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; Alkoxy anions having 1 to 20 carbon atoms; Carbonate anions having 1 to 20 carbon atoms; Alkylsulfonate anion having 1 to 20 carbon atoms; Amido (amide) anion having 1 to 20 carbon atoms; Carbamate anion having 1 to 20 carbon atoms; An anion of Meisenheimer's salt,

b and c satisfy the relation "(b + c) = (the total number of proton groups in L) + [(oxidation number of metal)-(number of X-type ligands in L)]".

The anion of Meisenheimer salt is a compound of the following structure.

Wherein R is methyl or hydrogen and R 'is selected from hydrogen or nitro (-NO ₂ ) but at least one of the five R's is nitro (-NO ₂ ).

In Formula 1, L-type and X-type ligands are described in detail in Organometallic Chemistry (published by Prentice Hall) p46 by Gary O. Spessard and Gary L. Miessler. L-type ligand means a neutral ligand and refers to a non-covalent electron pair donor such as phosphine, a pi bond donor such as ethylene, or a sigma bond donor such as hydrogen. L-type ligands bind to metals by providing non-covalent electron pairs, and the binding of L-type ligands does not affect the oxidation number of the metal. X-type ligand; refers to anionic ligands such as chlorine or methyl X ^- anion is deemed coupled to a metal element M ⁺ cations of the X-type ligand binding can affect the oxidation state of the metal.

According to another aspect of the present invention, a solution in which a copolymer and a catalyst obtained by the production method are dissolved is contacted with a solid inorganic material, a high molecular material, or a mixture thereof, which is not dissolved in the solution, thereby providing the solid inorganic material or polymer. Separating the copolymer by forming a complex of material and catalyst; And

In a medium in which the solid inorganic material or the polymer material cannot be dissolved, the catalyst is treated by treating the complex of the solid inorganic material or the polymer material with the catalyst with a metal salt of an acid or an unreactive anion to cause the catalyst to dissolve from the medium. Provided is a method for separating and recovering a catalyst from a solution in which a copolymer and a catalyst are dissolved, the method including separating and recovering.

According to another aspect of the invention, the complex is provided.

The present invention can consistently implement high activity and high selectivity by using a complex compound prepared from a ligand including a proton group and having a negative charge or higher divalent charge as a catalyst for a carbon dioxide / epoxide copolymerization reaction. . In addition, when carbon dioxide / epoxide copolymerization is performed using the complex compound according to the present invention as a catalyst, the ligand contains a proton group, thereby reducing the cost of the catalyst by separating and recovering and reusing the catalyst used after the copolymerization reaction to prepare a copolymer. In this case, economical efficiency can be realized, and by removing the catalyst which is a metal compound from the copolymer, it is possible to manufacture a copolymer having high purity, thereby expanding the range of use of the copolymer, and also improving the durability and processability of the copolymer. You can.

The complex used as the carbon dioxide / epoxide copolymerization catalyst according to the present invention is a complex compound coordinated by a monodentate, diedentate, or tridentate ligand comprising at least one proton group (i.e., a complex of Formula 1) As a complex, a metal center has an equilibrium structural formula capable of taking a negative divalent or higher form charge. The conventionally developed carbon dioxide / epoxide copolymerization catalyst is a techladentate (or quadradentate) simple-base complex with four groups attached to one metal, which is distinguished from the complex according to the invention.

The present invention is an alkylene oxide having 2 to 20 carbon atoms unsubstituted or substituted with halogen or alkoxy using a complex of the formula (1) as a catalyst; Cycloalkene oxide having 4 to 20 carbon atoms unsubstituted or substituted with halogen or alkoxy; And copolymerizing an epoxide compound selected from the group consisting of styrene oxides having 8 to 20 carbon atoms and unsubstituted or substituted with halogen, alkoxy, or alkyl, and carbon dioxide.

[Formula 1]

Wherein M is a metal element;

L is an L-type or X-type ligand;

a is 1, 2, or 3; When a is 1, L contains two or more proton groups, and when a is 2 or 3, each L may be the same or different from each other and may be connected to each other to form a bidentate or tridentate. Can be chelated to the metal as a ligand, at least one L contains at least one proton, and the total number of protons contained in L is at least 2,

Each X independently represents a halogen anion; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^-; HCO ₃ ^-; An aryloxy anion having 6 to 20 carbon atoms and a carboxy anion having 1 to 20 carbon atoms, with or without a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; Alkoxy anions having 1 to 20 carbon atoms; Carbonate anions having 1 to 20 carbon atoms; Alkylsulfonate anion having 1 to 20 carbon atoms; Amido (amide) anion having 1 to 20 carbon atoms; Carbamate anion having 1 to 20 carbon atoms; An anion of Meisenheimer's salt,

b and c satisfy the relation "(b + c) = (the total number of proton groups in L) + [(oxidation number of metal)-(number of X-type ligands in L)]".

In Formula 1, L-type and X-type ligands are described in detail in Organometallic Chemistry (published by Prentice Hall) p46 by Gary O. Spessard and Gary L. Miessler. L-type ligand means a neutral ligand and refers to a non-covalent electron pair donor such as phosphine, a pi bond donor such as ethylene, or a sigma bond donor such as hydrogen. L-type ligands bind to metals by providing non-covalent electron pairs, and the binding of L-type ligands does not affect the oxidation number of the metal. X-type ligand; refers to anionic ligands such as chlorine or methyl X ^- anion is deemed coupled to a metal element M ⁺ cations of the X-type ligand binding can affect the oxidation state of the metal.

According to one embodiment of the invention, the proton groups contained in the L is a functional group of the formula (2a), a functional group of the formula (2b), or a functional group of the formula (2c), M is a polycarbonate using a complex compound of cobalt trivalent or chromium trivalent Methods of making are provided:

(2a)

[Formula 2b]

[Formula 2c]

In Formulas 2a to 2c, Z is a nitrogen or phosphorus atom,

R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , R ²⁴ , and R ²⁵ each independently represent one or more of halogen, nitrogen, oxygen, silicon, sulfur, and phosphorus atoms. Alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl radical having 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl, two of R ¹¹ , R ¹² , and R ¹³ or R ²¹ , R ²² , R ²³ , R ²⁴ , and R ²⁵ Two of them may be linked together to form a ring,

R ³¹ , R ³² , and R ³³ are each independently hydrogen radical; Alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, with or without halogen atoms, nitrogen atoms, oxygen atoms, silicon atoms, sulfur atoms, and phosphorus atoms; Or arylalkyl radicals having 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl, two of R ³¹ , R ³² , and R ³³ may be linked to each other to form a ring,

X 'is an oxygen atom, a sulfur atom or NR (where R is a hydrogen radical; alkyl having 1 to 20 carbon atoms, with or without at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom) , Alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl radical having 7 to 20 carbon atoms.

According to another embodiment of the present invention, there is provided a method for producing a polycarbonate using a complex compound wherein L is a ligand of Formula 3, a is 2 or 3, and M is cobalt trivalent or chromium trivalent. do.:

(3)

Wherein A is oxygen or sulfur atom,

R ¹ to Each R ⁵ is independently: a hydrogen radical; Alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or without or including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom, or Arylalkyl radicals having 7 to 20 carbon atoms; A metalloid radical of a Group 14 metal substituted with hydrocarbyl, R ¹ to R ⁵ Two may be connected to each other to form a ring, R ¹ to At least one or more of R ⁵ includes one or more of Formula 2a, Formula 2b, and Formula 2c, and a is 2 or 3, and each L may be the same or different from each other, and is linked to each other to the bidentate or tridene. Tate ligands can be chelated to the metal.

According to another embodiment of the present invention, there is provided a process for preparing a polycarbonate wherein the catalyst is a complex of formula (4):

[Formula 4]

Wherein X is each independently a halogen anion; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^-; HCO ₃ ^-; An aryloxy anion having 6 to 20 carbon atoms and a carboxy anion having 1 to 20 carbon atoms, with or without a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; Alkoxy anions having 1 to 20 carbon atoms; Carbonate anions having 1 to 20 carbon atoms; Alkylsulfonate anion having 1 to 20 carbon atoms; Amido (amide) anion having 1 to 20 carbon atoms; Carbamate anion having 1 to 20 carbon atoms; An anion of Meisenheimer's salt,

R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ are hydrogen, tert-butyl, methyl, ethyl, isopropyl,-[YR ⁵¹ _3-m {(CR ⁵² R ⁵³ ) _n N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _m ], at least one of R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ is — [YR ⁵¹ _3-m {(CR ⁵² R ⁵³ ) _n N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _m ]. Wherein Y is a carbon or silicon atom, R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ are each independently hydrogen radical; Alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or without or including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom, or Arylalkyl radicals having 7 to 20 carbon atoms; A metalloid radical of a Group 14 metal substituted with hydrocarbyl, R ⁵⁴ , Two of R ⁵⁵ and R ⁵⁶ may be linked to each other to form a ring, m is an integer of 1 to 3, n is an integer of 1 to 20,

The value of b + c-1 is an integer equal to the sum of m of the total — [YR ⁵¹ _3-m {(CR ⁵² R ⁵³ ) _n N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _m ] included in the complex of Formula 4 Value.

In the complex of Formula 4, preferably R ⁴¹ , R ⁴³ , R ⁴⁴ , and R ⁴⁵ may be each independently selected from the group consisting of tert-butyl, methyl, ethyl, and isopropyl, and R ⁴² And R ⁴⁶ is — [CH {(CH ₂ ) ₃ N ⁺ Bu ₃ } ₂ ] and b + c may be 5.

According to another embodiment of the present invention, there is provided a process for preparing a polycarbonate wherein the catalyst is a complex of formula (5):

[Chemical Formula 5]

Wherein X is each independently a halogen anion; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^-; HCO ₃ ^-; An aryloxy anion having 6 to 20 carbon atoms and a carboxy anion having 1 to 20 carbon atoms, with or without a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; Alkoxy anions having 1 to 20 carbon atoms; Carbonate anions having 1 to 20 carbon atoms; Alkylsulfonate anion having 1 to 20 carbon atoms; Amido (amide) anion having 1 to 20 carbon atoms; Carbamate anion having 1 to 20 carbon atoms; An anion of Meisenheimer's salt,

R ⁶² and R ⁶⁴ are selected from tert-butyl, methyl, ethyl, isopropyl, or hydrogen, and R ⁶¹ and R ⁶³ are-[YR ⁵¹ _3-m {(CR ⁵² R ⁵³ ) _n N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _m ]. Where Y is a carbon or silicon atom, R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ are each independently hydrogen radical; Alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or without or including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom, or Arylalkyl radicals having 7 to 20 carbon atoms; A metalloid radical of a Group 14 metal substituted with hydrocarbyl, R ⁵⁴ , Two of R ⁵⁵ and R ⁵⁶ may be linked to each other to form a ring, m is an integer of 1 to 3, n is an integer of 1 to 20,

The value of b + c-1 is an integer value equal to twice the value of m,

A bridge is a daikal that connects two benzene rings.

According to another embodiment of the present invention, there is provided a process for preparing a polycarbonate, wherein the catalyst is a complex of formula (6):

[Formula 6]

Wherein X is each independently a halogen anion; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^-; HCO ₃ ^-; An aryloxy anion having 6 to 20 carbon atoms and a carboxy anion having 1 to 20 carbon atoms, with or without a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; Alkoxy anions having 1 to 20 carbon atoms; Carbonate anions having 1 to 20 carbon atoms; Alkylsulfonate anion having 1 to 20 carbon atoms; Amido (amide) anion having 1 to 20 carbon atoms; Carbamate anion having 1 to 20 carbon atoms; An anion of Meisenheimer's salt,

R ⁷² and R ⁷⁴ are selected from tert-butyl, methyl, ethyl, isopropyl, or hydrogen, R ⁷¹ and R ⁷³ are-[CH {(CH ₂ ) ₃ N ⁺ Bu ₃ } ₂ ] and b + c Is 5.

According to another embodiment of the present invention, there is provided a process for preparing a polycarbonate wherein the catalyst is a complex of formula:

[Formula 7]

Wherein Z is a carbon or silicon atom,

Each X independently represents a halogen anion; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^-; HCO ₃ ^-; An aryloxy anion having 6 to 20 carbon atoms and a carboxy anion having 1 to 20 carbon atoms, with or without a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; Alkoxy anions having 1 to 20 carbon atoms; Carbonate anions having 1 to 20 carbon atoms; Alkylsulfonate anion having 1 to 20 carbon atoms; Amido (amide) anion having 1 to 20 carbon atoms; Carbamate anion having 1 to 20 carbon atoms; An anion of Meisenheimer's salt,

R ⁸² and R ⁸⁴ are selected from tert-butyl, methyl, ethyl, isopropyl, or hydrogen, R ⁸¹ and R ⁸³ are-[CH {(CH ₂ ) ₃ N ⁺ Bu ₃ } ₂ ], b + c Is 5.

According to another embodiment of the present invention, there is provided a process for preparing a polycarbonate, wherein the catalyst is a complex of formula (8):

[Formula 8]

Wherein X is each independently a halogen anion; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^-; HCO ₃ ^-; An aryloxy anion having 6 to 20 carbon atoms and a carboxy anion having 1 to 20 carbon atoms, with or without a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; Alkoxy anions having 1 to 20 carbon atoms; Carbonate anions having 1 to 20 carbon atoms; Alkylsulfonate anion having 1 to 20 carbon atoms; Amido (amide) anion having 1 to 20 carbon atoms; Carbamate anion having 1 to 20 carbon atoms; An anion of Meisenheimer's salt,

R ⁹² and R ⁹⁴ are selected from methyl, ethyl, isopropyl, or hydrogen, R ⁹¹ and R ⁹³ are-[CH {(CH ₂ ) ₃ N ⁺ Bu ₃ } ₂ ],

Q is a di radical connecting two nitrogen atoms,

b + c is 5.

In the complex of Formula 8, preferably Q is trans-1,2-cyclohexylene or ethylene, and X may be 2,4-dinitrophenolate or BF ₄ ⁻ , respectively or simultaneously.

In the complex of Formula 8, R ⁹² and R ⁹⁴ are methyl, and R ⁹¹ and R ⁹³ are-[CH {(CH ₂ ) ₃ N ⁺ Bu ₃ } ₂ ] or-[CMe {( CH ₂ ) ₃ N ⁺ Bu ₃ } ₂ ], Q is trans-1,2-cyclohexylene or ethylene, b + c is 5, one of 5 X is BF ₄ , two are 2, 4-dinitrophenolate, two of which are anions of the formula (9).

[Formula 9]

Where R ¹⁰¹ is methyl or hydrogen.

Cobalt trivalent compounds prepared from Salen-type ligands containing four quaternary ammonium salts have different imine-coordinated coordination patterns, depending on their ligand structure, which differ from those of conventional four ligands. Can have Instead of imine, the counter anion of the quaternary ammonium salt is coordinated. This phenomenon has been identified in the present invention through ¹ H, ¹³ C, ¹⁵ N NMR spectroscopy, IR spectroscopy, DFT calculation, and cyclic voltammetric (CV). This extraordinary coordination pattern is that the substituent at position 3 of salicylic aldehyde, which is a component of the salen ligand, has no steric hindrance, such as methyl, and is not substituted with ethylenediamine, another component of the salen ligand, or cyclohexanediamine. Only one or two of the hydrogens attached to the four carbons are substituted to form when the steric hindrance of the metal coordination portion of the salen ligand is not large. On the other hand, a bulky substituent such as tert-butyl at salicyaldehyde, or hydrogen attached to four carbons of ethylenediamine is all substituted with methyl, resulting in high steric hindrance of the metal coordination portion of the salen ligand. When the conventional imine coordinated tetradentate compound is obtained. The figure below shows the differences in coordination patterns according to the structure of the salen ligand.

Exotic coordination compounds, such as 7, 5 and 10 , that are not coordinated by imine, show exceptionally high activity in carbon dioxide / epoxide copolymerization. On the other hand, compounds of tetradentate structure ( 6 , 8 , 10 ) dominated by conventional imines show no activity or low activity. NMR and CV studies have shown that tetradentate-structured compounds immobilized by conventional imines are readily reduced to cobalt divalent compounds compared to compounds of a different coordination mode that imine is not coordinated. Cobalt divalent compounds are inactive for carbon dioxide / epoxide copolymerization.

The coordination state of the anion in the different coordination mode compounds not immigrated is related to temperature, solvent, and ligand structure, particularly by NMR spectroscopy at THF-d ₈ , which is most similar to the polymerization medium. In the compounds 5 , 7 , and 10 (X = 2,4-dinitrophenolate, hereinafter referred to as DNP), two DNPs are always coordinating to cobalt, and two are constantly coming and going in coordination and decoordination states. Typically of 6 coordination body trivalent cobalt compound it is known in the diamagnetic andago inactive ligand substitution reaction (Becker, CAL;... .. Motladiile, S. Synth React Inorg Met .- Org Chem 2001, 31, 1545.) . However, in a novel coordination mode compound which is not coordinated with the imine of the present invention, cobalt has a negative charge and can decoordinate a ligand having a negative charge. The negatively charged decoordinated ligand is held together with the cation of the quaternary ammonium salt and cannot escape far from cobalt. Fundamentally uncoordinated anions are thermodynamically unstable species that tend to coordinate back to cobalt. The combination of these two trends gives two DNPs the ability to constantly move in and out of coordination and decoordination states. Several coordinating cobalt trivalent compounds with negative cobalt have been reported ((a) Collins, TJ; Richmond, TG; Santarsiero, BD; Treco BGRT J. Am. Chem. Soc. 1986 , 108 , 2088 (b) Gray, HB; Billig, E. J. Am. Chem. Soc. 1963 , 85 , 2019.). The addition of anionic or neutral ligands in addition to compounds of this structure has been reported to readily switch between 4-, 5-, and 6-configurations ((a) Langford, CH; Billig, E .; Shupack, SI; Gray, HB J. Am. Chem. Soc. 1964 , 86 , 2958; (b) Park, J .; Lang, K .; Abboud, KA; Hong, S. J. Am. Chem. Soc. 2008 , 130 , 16484.). The unusual coordination of compounds of the present invention, which are not coordinated by the imine of the present invention, exhibits unusually high activity due to the property that the ligands of the two anions observed can constantly move between the coordination and decoordination states. The figure below shows the mechanism by which the polymer chains of carbon dioxide / epoxide copolymerization grow. In this mechanism, the step of attacking the coordinated epoxide of the carbonate anion formed at the chain end is important. The ability to constantly move back and forth between the coordination and decoordination states makes it possible to attack behind the coordinated epoxides of carbonate anions. Nucleophilic attack usually occurs by attack behind a leaving group. The difference in activity can be seen depending on how much easier anion can be decoordinated from cobalt, which is constantly in and out of the coordinating state. Analysis by NMR spectroscopy shows that the binding affinity sequence of anions constantly shifting between coordination and decoordination states is 5 > 10 > 7 . The magnitude of the activity was observed in the reverse order.

In the carbon dioxide / epoxide copolymerization catalyst reaction using a different coordination type of compound which is not imine-coordinated, the [water] / [catalyst] ratio of the polymerization reaction system plays an important role in implementing the catalytic activity. Even if the epoxide and carbon dioxide are thoroughly purified to remove water, the ratio of [water] / [catalyst] may be significant under polymerization conditions in which the [epoxide] / [catalyst] ratio is considerably less catalyst such as 100,000 or 150,000. There is this. High activity (TON) can be obtained only when the [epoxide] / [catalyst] ratio is able to implement the polymerization at high conditions such as 100,000 or 150,000. Therefore, to be a commercially available catalyst, the catalyst must be less sensitive to water. In the case of catalysts of the 5 , 7 and 10 structures, the induction time is observed to vary greatly depending on the degree of lack of water in the polymerization system. In other words, when the polymerization reaction is carried out in the dry winter, the polymerization reaction starts after about 1 to 3 hours, but when polymerization is carried out in the summer with high humidity and high temperature, the polymerization starts after 12 hours. Once the polymerization reaction started, the activity (TOF) did not differ significantly. ^{In the 1} H NMR spectroscopy experiment, the reaction of the compound containing DNP attacking propylene oxides is observed, and the reaction rate is observed to drop rapidly when water exists to some extent. It is inferred that the anion, which is constantly in the coordinating and decoordinating state, is hydrogen-bonded with water, causing the nucleophile attack ability to be lowered, resulting in a slow reaction rate.

This phenomenon, in which the induction time changes depending on the degree of dryness, becomes a burden of commercialization to constantly control the level of dryness. This problem is alleviated to some extent by synthesizing the 14 compound of Scheme as a catalyst. Compound 14 can be prepared under conditions where the ratio of [flophilene oxide] / [catalyst] is very low (1,000 or less). In this case, the amount of water remaining in the flopylene oxide is not significant compared to the amount of the catalyst. In other words, the [water] / [catalyst] ratio is adjusted very low to produce 14 consistently. 14 compounds can also be stored and used as catalysts. 14 In the case of compounds, the anion, which is constantly in the coordination and decoupling state, has reacted with puffylene oxide, which reduces the sensitivity to water, resulting in a consistent induction time (1-2 hours). In addition, even under the condition that the [epoxide] / [catalyst] ratio is 150,000, polymers exhibit a polymerization reactivity (TOF, 80,000 h ⁻¹ ) with a short induction time (70 min), thereby enabling higher TON (20,000). In the case of 10 compounds, polymerization activity was not realized under the condition that the [epoxide] / [catalyst] ratio was 150,000.

It is also possible to obtain a compound having the same structure as the 14 structure in which the propylene oxide of the above reaction reacts with 14 structures in which two DNPs are converted into anions of Meisenheimer's salt. In the case of a compound with a different coordination mode that is not coordinated by the imine of the present invention, two DNPs are coordinating strongly with cobalt, and the other two are constantly coordinating with and out of coordination state. Only DNP, which is constantly in and out of the coordination state, reacts quickly with propylene oxide to give a compound of 14 structures after 1 hour. On the other hand, in the case of the tetradentate Salen-Co (III) compound which is imine coordinated as in 6 , 8 and 11 , when propylene oxide is reacted, only two DNPs are converted to the anion of Meisenheimer's salt like 14 compound. And the rest of the DNP continues to be converted to the anion of Meisenheimer's salt. In particular, in the reaction of propylene oxide, as described above, the reaction with the cobalt divalent compound is considerably entailed, so that like the compound 14, two DNPs are intact and two are not obtained in the form of pure compounds converted into anions of Meisenheimer's salt. . 14 compounds can also be prepared by anionic substitution reactions such as the following reactions. In this anion-friendly reaction, one of the anions of the substituted Meisenheimer salt is converted into DNP. The cobalt reduction reaction was the main reaction when the same anion-aromatic reaction was carried out to the compound from which the structure of the tetradentate Salen-Co (III) compound in which imine was coordinated, such as 6 , 8 , and 11 , was obtained.

Specific examples of epoxide compounds that can be used in the copolymerization of the present invention include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, Octadecene oxide, butadiene monoxide, 1,2-epoxide-7-octene, epifluorohydrin, epichlorohydrin, epibromohydrin, isopropyl glycidyl ether, butyl glycidyl ether, t -Butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3-epoxy Sidnorbornene, limonene oxide, dieldrin, 2,3-epoxidepropylbenzene, styrene oxide, phenyl Propylene oxide, stilbene oxide, chlorostilbene oxide, dichlorostilbene oxide, 1,2-epoxide-3-phenoxypropane, benzyloxymethyl oxirane, glycidyl-methylphenyl ether, chlorophenyl-2,3- Epoxidepropyl ether, epoxypropyl methoxyphenyl ether, biphenyl glycidyl ether, glycidyl naphthyl ether and the like. The epoxide compound may be copolymerized with carbon tetrachloride alone or by mixing 2-4.

Epoxide compounds may be used for polymerization using an organic solvent as a reaction medium, and as the solvent, aliphatic hydrocarbons such as pentane, octane, decane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, chloromethane, methylene chloride , Chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, ethylchloride, trichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1 It may be used alone or in combination of two or more of halogenated hydrocarbons such as -chloro-2-methylpropane, chlorobenzene and bromobenzene. More preferably, bulk polymerization using the monomer itself as a solvent can be performed.

The molar ratio of epoxide compound to catalyst, ie the epoxide compound: catalyst molar ratio, can be used at 1,000 to 1,000,000, preferably at 50,000 to 200,000. At this time, the conversion rate of the catalyst, that is, the number of moles of the epoxide compound consumed per mole of cobalt per hour can be realized more than 500 turnover / hr. The pressure of carbon dioxide can be up to 100 atmospheres at normal pressure, preferably from 5 atmospheres to 30 atmospheres. Polymerization temperature is possible from 20 degreeC to 120 degreeC, Preferably 50 degreeC-90 degreeC is suitable.

As a method of polymerizing a polycarbonate, it can manufacture by a batch polymerization method, a semi-batch polymerization method, or a continuous polymerization method. In the case of using a batch or semibatch polymerization method, the reaction time can be 1 to 24 hours, preferably 1.5 to 4 hours. In the case of using the continuous polymerization method, the average residence time of the catalyst is also preferably set to 1.5 to 4 hours.

According to the present invention, a polycarbonate having a number average molecular weight (M _n ) having a molecular weight of 5,000 to 1,000,000 and a molecular weight distribution (ie, M _w / M _n ) having a value of 1.05 to 4.0 can be produced. Here, M _n means the number average molecular weight measured by GPC by correcting the polystyrene of a single molecular weight distribution with a standard material, the molecular weight distribution M _w / M _n value is the weight average molecular weight and number average specified by GPC by the same method The ratio between the molecular weights.

The polycarbonate polymers produced are composed of at least 80% carbonate bonds and often at least 95% carbonate bonds. This polycarbonate material is a polymer which is easy to decompose and is free of residue and soot during combustion, for example, a material useful as a packaging material, a heat insulating material, or a coating material.

The present invention is a composite of the solid inorganic material or the polymer material and the catalyst by contacting the solution obtained by the above method with the copolymer and the catalyst is dissolved in a solid inorganic material, a high molecular material or a mixture thereof which is not dissolved in the solution Separating the copolymer by forming a; And in a medium in which the solid inorganic material or the polymeric material cannot be dissolved, the catalyst is treated by treating the complex of the solid inorganic material or the polymeric material with a catalyst with a metal salt of an acid or an unreactive anion to cause the catalyst to dissolve from the medium. And separating and recovering the catalyst from the solution in which the copolymer and the catalyst are dissolved.

The "solution in which the copolymer and the catalyst are dissolved" is a solution obtained in the step of not removing the remaining carbon dioxide and epoxide after the polymerization reaction described above, a solution obtained by removing only carbon dioxide, or a polymerization reaction. After removal of both the carbon dioxide and epoxide may be a solution obtained by putting another solvent again for post-treatment. Methylene chloride, THF, etc. are preferable as a solvent that can be used for the workup.

The contact between the solution in which the copolymer and the catalyst are dissolved and the solid inorganic material, the polymer material or a mixture thereof is added to the solution in which the copolymer and the catalyst are dissolved. This can be done by filtration or by passing the solution in which the copolymer and the catalyst are dissolved through a column packed with a solid inorganic material, a high molecular material or a mixture thereof. The solid phase inorganic material may be surface modified or unmodified silica or alumina, and the solid phase material may be a high molecular material having a functional group capable of deprotonation reaction by an alkoxy anion. The functional groups in which the proton reaction can occur can be sulfonic acid groups, carboxylic acid groups, phenol groups or alcohol groups.

The solid polymer is preferably crosslinked with a number average molecular weight of 500 to 10,000,000, but is not dissolved in a solution containing a copolymer and a catalyst even if not crosslinked. More specific examples of "a solid polymer material having a functional group capable of deprotonation reaction by an alkoxy anion" include copolymers containing monomers such as the following Chemical Formulas 10a to 10e or homopolymers composed only of such monomers. homopolymer). The polymer material acting as such a support may be uncrosslinked as long as it does not dissolve in the above-described solution, but is preferably crosslinked appropriately to reduce solubility.

[Formula 10a]

[Formula 10b]

[Formula 10c]

[Formula 10d]

[Formula 10e]

According to an embodiment of the present invention, the copolymer obtained by the method for preparing a carbon dioxide / epoxide copolymer using the catalyst and the solution in which the catalyst is dissolved are contacted with silica to form a silica-catalyst complex to separate the copolymer. Making; And separating and recovering the catalyst by treating the silica-catalyst complex with a metal salt of an acid or non-reactive anion to dissolve the catalyst from the medium, in a medium incapable of dissolving the silica. A method for separating and recovering a catalyst from a solution in which is dissolved is provided. The acid may be this 2,4-dinitrophenol and the metal salt of the non-reactive anion may be MBF ₄ , where M is Li, Na or K.

Scheme 1 below shows the mechanism of catalyst separation and recovery reaction. When copolymerizing the epoxide and carbon dioxide using the complex as a catalyst, the anion of the ammonium salt is coordinated to the metal to nucleophile attack the activated epoxide to initiate the reaction. The alkoxy anion formed upon nucleophilic attack reacts with carbon dioxide to form a carbonate anion, which in turn nucleophilizes an epoxide coordinated with a metal to form a carbonate anion, and the reaction is repeated to form a polymer chain. In this case, some or all of the anions of the ammonium salts contained in the catalyst are converted to carbonate anions or alkoxide anions containing polymer chains. Removing carbon dioxide after the polymerization reaction converts the carbonate anion to an alkoxide anion. After polymerization, the solution in which the catalyst and the copolymer are dissolved is contacted with the above-mentioned "polymer material having a functional group capable of deprotonation reaction by an alkoxy anion" or a solid material having hydroxyl groups on the surface such as silica or alumina. As a result, as shown in Scheme 1, the polymer chain is protonated and dissolved in the solution by the acid-base reaction, and the catalyst component forms a complex with a solid inorganic material or a polymer material. This complex can be easily separated by filtration from the copolymer because it is insoluble.

Scheme 1

The catalyst can be recovered and reused from a complex of a solid inorganic material or a polymer material and a catalyst separated and recovered by filtration. The solid inorganic or polymeric complexes with the catalyst are not soluble in conventional solvents. However, in a medium in which an inorganic material or a polymer material cannot be dissolved, when the metal complex of an acid or non-reactive anion is treated to the recovered complex, the catalyst is dissolved in the medium by an acid-base reaction or a salt metathesis reaction. This may be filtered to desorb and recover the catalyst component from a solid inorganic or polymeric material. At this time, the PKa value of the treated acid should have a value less than or equal to the PKa value of the anion formed on the support. The preferred acid to be treated is advantageous in that it must be selected so that the counterbase of the acid exhibits excellent performance in realizing the activity in the polymerization reaction. Preferred as such acids are HCl and 2,4-dinitrophenol. Cl anions and 2,4-dinitrophenolate anions are known to exhibit high activity and high selectivity during polymerization. Preferred as salts of non-reactive anions are DBF ₄ or DClO ₄ , where D is Li, Na or K. When the salt of the non-reactive anion is treated, the compound containing the non-reactive anion is dissolved. This non-reactive anion may be substituted by a salt metathesis reaction with a Cl anion and a 2,4-dinitrophenolate anion showing high activity and high selectivity. The process of recovering the catalyst is carried out under a suitable solvent in which the catalyst is dissolved and the inorganic or polymeric material is not dissolved. Preferred such solvents are methylene chloride, ethanol or methanol.

The metal content of the resin can be lowered to 15 ppm or less by removing the catalyst after polymerization in the above manner. Accordingly, the present invention provides a copolymer having a metal content of 15 ppm or less separated from the solution in which the copolymer and the catalyst are dissolved as described above. If the catalyst is not separated from the resin by the above method, the resin becomes colored due to the inclusion of a metal compound, which is an obstacle to commercialization. In addition, most of the transition metals are toxic, so if the metal is not removed, it is a big problem in the development of the resin. In addition, if the polymer solution is not treated by the above method and the protons are not attached to the terminal of the polymer chain after polymerization, the polymer may be easily formed by the Beck-byte reaction as shown in Scheme 2 below when the temperature of the resin is slightly increased or the resin is stored for a long time. Converted to a single molecule. This causes a big problem in the processing of the resin, and the durability of the resin is greatly lowered, making it impossible to use commercially. When the polymer solution is treated after polymerization by the above method, protons are attached to the terminals of the polymer chain, and the alkoxide anion is changed to an alcohol group, and the alcohol group is weaker than the alkoxide anion, so that the Beckite reaction of Scheme 2 does not occur, thereby providing processability to the resin. And durability is strong.

Scheme 2

The present invention provides a complex of formula 4 useful as a catalyst:

[Formula 4]

Wherein X is each independently a halogen anion; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^-; HCO ₃ ^-; An aryloxy anion having 6 to 20 carbon atoms and a carboxy anion having 1 to 20 carbon atoms, with or without a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; Alkoxy anions having 1 to 20 carbon atoms; Carbonate anions having 1 to 20 carbon atoms; Alkylsulfonate anion having 1 to 20 carbon atoms; Amido (amide) anion having 1 to 20 carbon atoms; Carbamate anion having 1 to 20 carbon atoms; An anion of Meisenheimer's salt,

R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ are hydrogen, tert-butyl, methyl, ethyl, isopropyl,-[YR ⁵¹ _3-m {(CR ⁵² R ⁵³ ) _n N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _m ], at least one of R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ is — [YR ⁵¹ _3-m {(CR ⁵² R ⁵³ ) _n N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _m ]. Wherein Y is a carbon or silicon atom, R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ are each independently hydrogen radical; Alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or without or including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom, or Arylalkyl radicals having 7 to 20 carbon atoms; A metalloid radical of a Group 14 metal substituted with hydrocarbyl, R ⁵⁴ , Two of R ⁵⁵ and R ⁵⁶ may be linked to each other to form a ring, m is an integer of 1 to 3, n is an integer of 1 to 20,

The value of b + c-1 is an integer equal to the sum of m of the total — [YR ⁵¹ _3-m {(CR ⁵² R ⁵³ ) _n N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _m ] included in the complex of Formula 4 Value.

In the complex of Formula 4, preferably R ⁴¹ , R ⁴³ , R ⁴⁴ , and R ⁴⁵ may be each independently selected from the group consisting of tert-butyl, methyl, ethyl, and isopropyl, and R ⁴² And R ⁴⁶ is — [CH {(CH ₂ ) ₃ N ⁺ Bu ₃ } ₂ ] and b + c may be 5.

According to one embodiment of the present invention, a complex of formula 5 is provided:

[Chemical Formula 5]

Wherein X is each independently a halogen anion; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^-; HCO ₃ ^-; An aryloxy anion having 6 to 20 carbon atoms and a carboxy anion having 1 to 20 carbon atoms, with or without a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; Alkoxy anions having 1 to 20 carbon atoms; Carbonate anions having 1 to 20 carbon atoms; Alkylsulfonate anion having 1 to 20 carbon atoms; Amido (amide) anion having 1 to 20 carbon atoms; Carbamate anion having 1 to 20 carbon atoms; An anion of Meisenheimer's salt,

R ⁶² and R ⁶⁴ are selected from tert-butyl, methyl, ethyl, isopropyl, or hydrogen, and R ⁶¹ and R ⁶³ are-[YR ⁵¹ _3-m {(CR ⁵² R ⁵³ ) _n N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _m ]. Where Y is a carbon or silicon atom, R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ are each independently hydrogen radical; Alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or without or including at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom, or Arylalkyl radicals having 7 to 20 carbon atoms; A metalloid radical of a Group 14 metal substituted with hydrocarbyl, R ⁵⁴ , Two of R ⁵⁵ and R ⁵⁶ may be linked to each other to form a ring, m is an integer of 1 to 3, n is an integer of 1 to 20,

The value of b + c-1 is an integer value equal to twice the value of m,

A bridge is a daikal that connects two benzene rings.

According to another embodiment of the present invention, a complex of formula 6 is provided:

[Formula 6]

Wherein X is each independently a halogen anion; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^-; HCO ₃ ^-; An aryloxy anion having 6 to 20 carbon atoms and a carboxy anion having 1 to 20 carbon atoms, with or without at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; Alkoxy anions having 1 to 20 carbon atoms; Carbonate anions having 1 to 20 carbon atoms; Alkylsulfonate anion having 1 to 20 carbon atoms; Amido (amide) anion having 1 to 20 carbon atoms; Carbamate anion having 1 to 20 carbon atoms; An anion of Meisenheimer's salt,

R ⁷² and R ⁷⁴ are selected from tert-butyl, methyl, ethyl, isopropyl, or hydrogen, R ⁷¹ and R ⁷³ are-[CH {(CH ₂ ) ₃ N ⁺ Bu ₃ } ₂ ] and b + c Is 5.

According to another embodiment of the present invention, a complex of formula 7 is provided:

[Formula 7]

Wherein Z is a carbon or silicon atom,

Each X independently represents a halogen anion; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^-; HCO ₃ ^-; An aryloxy anion having 6 to 20 carbon atoms, a carboxy anion having 1 to 20 carbon atoms, or without a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; Alkoxy anions having 1 to 20 carbon atoms; Carbonate anions having 1 to 20 carbon atoms; Alkylsulfonate anion having 1 to 20 carbon atoms; Amido (amide) anion having 1 to 20 carbon atoms; Carbamate anion having 1 to 20 carbon atoms; An anion of Meisenheimer's salt,

R ⁸² and R ⁸⁴ are selected from tert-butyl, methyl, ethyl, isopropyl, or hydrogen, R ⁸¹ and R ⁸³ are-[CH {(CH ₂ ) ₃ N ⁺ Bu ₃ } ₂ ], b + c Is 5.

According to another embodiment of the present invention, a complex of formula 8 is provided:

[Formula 8]

Wherein X is each independently a halogen anion; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^-; HCO ₃ ^-; An aryloxy anion having 6 to 20 carbon atoms and a carboxy anion having 1 to 20 carbon atoms, with or without at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom; Alkoxy anions having 1 to 20 carbon atoms; Carbonate anions having 1 to 20 carbon atoms; Alkylsulfonate anion having 1 to 20 carbon atoms; Amido (amide) anion having 1 to 20 carbon atoms; Carbamate anion having 1 to 20 carbon atoms; An anion of Meisenheimer's salt,

R ⁹² and R ⁹⁴ are selected from methyl, ethyl, isopropyl, or hydrogen, R ⁹¹ and R ⁹³ are-[CH {(CH ₂ ) ₃ N ⁺ Bu ₃ } ₂ ],

Q is a di radical connecting two nitrogen atoms,

b + c is 5.

In the complex of Formula 8, preferably Q is trans-1,2-cyclohexylene or ethylene, and X may be 2,4-dinitrophenolate or BF ₄ ⁻ , respectively or simultaneously.

In the complex of Formula 8, more preferably R ⁹² and R ⁹⁴ are methyl, R ⁹¹ and R ⁹³ are-[CH {(CH ₂ ) ₃ N ⁺ Bu ₃ } ₂ ], and Q is trans- 1,2-cyclohexylene or ethylene, b + c is 5, one of 5 X is BF ₄ , two are 2,4-dinitrophenolate, two are anions of Formula 9 to be.

[Formula 9]

Where R ¹⁰¹ is methyl or hydrogen.

The complex according to the present invention is prepared by first synthesizing a ligand containing an ammonium salt and coordinating it in cobalt as shown in Scheme 3 below. As a typical method of attaching metals, cobalt acetate (Co (OAc) ₂ ) is reacted with a ligand to decoordinate the acetate ligand to remove acetic acid to obtain a cobalt divalent compound, which is a suitable acid (HX; X is X in Formula 1). And cobalt trivalent compounds in the presence of oxygen. Ligands containing ammonium salts are prepared according to known methods developed and disclosed by the inventors ( J. Am . Chem . Soc . 2007 , 129 , 8082; Angew . Chem . Int . Ed . , 2008 , accepted.) can do.

Scheme 3

The present invention will be described in more detail with reference to the following examples. However, the following examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.

[ Example  1] 3- methyl -5-[{ BF ₄ ^- This ₃ N ⁺ ( CH ₂ ) ₃ } ₂ CH }]-Salylaldehyde Compound Synthesis

The title compound was prepared by hydrolysis of the ligand of Formula 11a. Compounds of formula 11a were synthesized according to methods known by the inventors ( Angew . Chem . Int . Ed . , 2008 , accepted).

[Formula 11a]

The compound of Formula 11a (0.500 g, 0.279 mmol) was dissolved in methylene chloride (4 mL), HI aqueous solution (2 N, 2.5 mL) was added thereto, and the mixture was stirred at 70 ° C. for 3 hours. The water layer was removed and the methylene chloride layer was washed with water, then dried with anhydrous magnesium chloride and then the solvent was removed under reduced pressure. Purified by silica gel column chromatography with methylene chloride / ethanol (10: 1) mixed solution to give 0.462 g of 3-methyl-5-[{I ^- Bu ₃ N ⁺ (CH ₂ ) ₃ } ₂ CH}]-salicylic Aldehyde was obtained (yield, 95%). This compound was taken up in ethanol (6 mL) and AgBF ₄ (0.225 g, 1.16 mmol) was added thereto. The mixture was stirred at room temperature for 1.5 hours and then filtered. Under reduced pressure to remove the solvent, and then methylene chloride / ethanol (10: 1) purification by column chromatography on silica gel with a mixed solution of 0.410 g 3- methyl ^{_{-5 - [{BF 4 - Bu}} 3 N + (CH 2) 3} ₂ CH}]-salicyaldehyde compound (100%).

¹ H NMR (CDCl ₃ ): δ 11.19 (s, 1H, OH), 9.89 (s, 1H, CHO), 7.48 (s, 1H, m- H), 7.29 (s, 1H, m- H), 3.32 -3.26 (m, 4H, -NCH ₂ ), 3.10-3.06 (m, 12H, -NCH ₂ ), 2.77 (septet, J = 6.8 Hz, 1H, -CH-), 2.24 (s, 3H, -CH ₃ ), 1.76-1.64 (m, 8H, -CH ₂ ), 1.58-1.44 (m, 16H, -CH ₂ ), 1.34-1.29 (m, 8H, -CH ₂ ), 0.90 (t, J = 7.6 Hz, 18H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ 197.29, 158.40, 136.63, 133.48, 130.51, 127.12, 119.74, 58.23, 40.91, 32.51, 23.58, 19.48, 18.82, 15.10, 13.45 ppm.

Example 2 3-t-butyl-5-[{BF ₄ ^- This ₃ N ⁺ (CH ₂ ) ₃ } ₂ CH}]-salicylate compound synthesis

Using the compound of formula 11b, the title compound was prepared in the same manner as in Example 1. Compounds of formula 11b were also synthesized according to methods known by the inventors ( Angew . Chem. Int . Ed . , 2008 , accepted).

[Formula 11b]

¹ H NMR (CDCl ₃ ): δ 11.76 (s, 1H, OH), 9.92 (s, 1H, CHO), 7.53 (s, 1H, m -H), 7.35 (s, 1H, m -H), 3.36 -3.22 (m, 16H, -NCH ₂ ), 2.82 (br, 1H, -CH-), 1.78-1.70 (m, 4H, -CH ₂ ), 1.66-1.46 (m, 16H, -CH ₂ ), 1.42 (s, 9H, -C (CH ₃ ) ₃ ), 1.38-1.32 (m, 12H, butyl -CH ₂ ), 0.93 (t, J = 7.6 Hz, 18H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ 197.76, 159.67, 138.70, 133.50, 132.63, 131.10, 120.40, 58.55, 41.45, 34.99, 32.28, 29.31, 23.72, 19.59, 19.00, 13.54 ppm.

[ Example  3] Synthesis of Complex 7

Scheme 4 below summarizes the method of synthesis of the complex.

Scheme 4

Ethylenediamine dihydrochloride (10 mg, 0.074 mmol), sodium t-butoxide (14 mg), and 3-methyl-5-[{BF ₄ ^- Bu ₃ N ⁺ (CH ₂ ) prepared in Example 1 ₃ } ₂ CH}]-salicyaldehyde compound (115 mg) was weighed in a bayer in a dry box, and ethanol (2 mL) was added thereto, followed by stirring at room temperature overnight. The reaction mixture was filtered, the filtrate was taken and ethanol was removed under reduced pressure. Dissolved again in methylene chloride and filtered once more. The solvent was removed under reduced pressure, followed by addition of Co (OAc) ₂ (13 mg, 0.074 mmol) and ethanol (2 mL). The reaction mixture was stirred at room temperature for 3 hours and then the solvent was removed under reduced pressure. The obtained compound was washed twice with diethyl ether (2 mL) to obtain a solid compound. This solid compound was dissolved in methylene chloride (2 mL) again, and 2,4-dynitrophenol (14 mg, 0.074 mmol) was added, followed by stirring for 3 hours in the presence of oxygen. Sodium 2,4-dinitrophenolate (92 mg, 0.44 mmol) was added to the reaction mixture, and the mixture was stirred overnight. Filtration with celite and removal of solvent gave a dark brown solid compound (149 mg, 100%). ¹ H NMR (dmso-d _{6 ,} 40 ^o C): δ 8.84 (br, 2H, (NO ₂ ) ₂ C ₆ H ₃ O), 8.09 (br, 2H, (NO ₂ ) ₂ C ₆ H ₃ O) , 8.04 (s, 1H, CH = N), 7.12 (s, 2H, m- H), 6.66 (br, 2H, (NO ₂ ) ₂ C ₆ H ₃ O), 4.21 (br, 2H, ethylene-CH ₂ ), 3.35-2.90 (br, 16H, NCH ₂ ), 2.62 (s, 3H, CH ₃ ), 1.91 (s, 1H, CH), 1.68-1.42 (br, 20H, CH ₂ ), 1.19 (br, 12H, CH ₂ ), 0.83 (br, 18H, CH ₃ ) ppm. ¹ H NMR (THF-d _{8 ,} 20 ^o C): δ 8.59 (br, 1H, (NO ₂ ) ₂ C ₆ H ₃ O), 8.10 (br, 1H, (NO ₂ ) ₂ C ₆ H ₃ O) , 7.93 (s, 1H, CH = N), 7.88 (br, 1H, (NO ₂ ) ₂ C ₆ H ₃ O), 7.05 (s, 1H, m -H), 6.90 (s, 1H, m -H ), 4.51 (s, 2H, ethylene-CH ₂ ), 3.20-2.90 (br, 16H, NCH ₂ ), 2.69 (s, 3H, CH ₃ ), 1.73 (s, 1H, CH), 1.68-1.38 (br , 20H, CH ₂ ), 1.21 (m, 12H, CH ₂ ), 0.84 (t, J = 6.8 Hz, 18H, CH ₃ ) ppm. ¹ H NMR (CD ₂ Cl _{2 ,} 20 ^o C): δ 8.43 (br, 1H, (NO ₂ ) ₂ C ₆ H ₃ O), 8.15 (br, 1H, (NO ₂ ) ₂ C ₆ H ₃ O) , 7.92 (br, 1H, (NO ₂ ) ₂ C ₆ H ₃ O), 7.79 (s, 1H, CH = N), 6.87 (s, 1H, m -H), 6.86 (s, 1H, m -H ), 4.45 (s, 2H, ethylene-CH ₂ ), 3.26 (br, 2H, NCH ₂ ), 3.0-2.86 (br, 14H, NCH ₂ ), 2.65 (s, 3H, CH ₃ ), 2.49 (br, 1H, CH), 1.61-1.32 (br, 20H, CH ₂ ), 1.31-1.18 (m, 12H, CH ₂ ), 0.86 (t, J = 6.8 Hz, 18H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (dmso-d ₆ , 40 ^o C): δ 170.33, 165.12, 160.61, 132.12 (br), 129.70, 128.97, 127.68 (br), 124.51 (br), 116.18 (br), 56.46 , 40.85, 31.76, 21.92, 18.04, 16.16, 12.22 ppm. ¹⁵ N { ¹ H} NMR (dmso-d ₆ , 20 ^o C): δ -156.32, -159.21 ppm. ¹⁵ N { ¹ H} NMR (THF-d _{8 ,} 20 ^o C): δ -154.19 ppm. ¹⁹ F { ¹ H} NMR (dmso-d ₆ , 20 ^o C): δ -50.63, -50.69 ppm.

Example 4 Synthesis of Complex Compound 8

Using the 3-t-butyl-5-[{BF ₄ ^- Bu ₃ N ⁺ (CH ₂ ) ₃ } ₂ CH}]-salicylaldehyde prepared in Example 2 in the same manner as in Example 3 It was. ¹ H NMR (dmso-d ₆ , 40 ^o C): δ 8.82 (br, 2H, (NO ₂ ) ₂ C ₆ H ₃ O), 7.89 (br, 3H, (NO ₂ ) ₂ C ₆ H ₃ O, CH = N), 7.21 (s, 1H, m- H), 7.19 (s, 1H, m- H), 6.46 (br, 4H, (NO ₂ ) ₂ C ₆ H ₃ O), 4.12 (s, 2H , ethylene-CH ₂ ), 3.25-2.96 (br, 16H, NCH ₂ ), 1.90 (s, 1H, CH), 1.71 (s, 9H, C (CH ₃ ) ₃ ), 1.67-1.32 (br, 20H, CH ₂ ), 1.32-1.15 (m, 12H, CH ₂ ), 0.88 (t, J = 7.2 Hz, 18H, CH ₃ ) ppm. ¹ H NMR (THF-d _{8 ,} 20 ^o C): δ 7.78 (s, 1H, CH = N), 7.31 (s, 1H, m -H), 7.12 (s, 1H, m -H), 4.19 ( br, 2H, ethylene-CH ₂ ), 3.43-2.95 (br, 16H, NCH ₂ ), 2.48 (br, 1H, CH), 1.81-1.52 (br, 20H, CH ₂ ), 1.50 (s, 9H, C (CH ₃ ) ₃ ), 1.42-1.15 (br, 12H, CH ₂ ), 0.89 (t, J = 6.8 Hz, 18H, CH ₃ ) ppm. ¹ H NMR (CD ₂ Cl _2, 20 ^o C): δ 7.47 (s, 1H, CH = N), 7.10 (s, 1H, mH), 7.07 (s, 1H, mH), 4.24 (s, 2H, ethylene-CH ₂ ), 3.31 (br, 2H, NCH ₂ ), 3.09-2.95 (br, 14H, NCH ₂ ), 2.64 (br, 1H, CH), 1.68-1.50 (br, 20H, CH ₂ ), 1.49 (s, 9H, C (CH ₃ ) ₃ ), 1.39-1.26 (m, 12H, CH ₂ ), 0.93 (t, J = 6.8 Hz, 18H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (dmso-d ₆ , 40 ^o C): δ 166.57, 166.46, 161.55, 142.16, 129.99, 129.26, 128.39, 128.13, 127.63, 124.18, 118.34, 56.93, 41.64, 34.88, 32.27, 29.63 , 22.37, 18.64, 18.51, 12.70 ppm. ¹⁵ N { ¹ H} NMR (dmso-d ₆ ): -163.43 ppm. ¹⁵ N { ¹ H} NMR (THF-d _{8 ,} 20 ^o C): δ -166.80 ppm. ¹⁹ F { ¹ H} NMR (dmso-d ₆ , 20 ^o C): δ -50.65, -50.70 ppm.

[ Example  5] Synthesis of Complex 9

It synthesized according to Scheme 5 below.

Scheme 5

17 Synthesis

1-chloro-4-iodobutane (1.00 g, 4.57 mmol) was dissolved in a mixture of diethyl ether / pentane (2: 3) to a concentration of 0.10 M, and then -78. ^o Lower the temperature to C and slowly add t-butyllithium (3.690 g, 9.610 mmol, 1.7 M pentane solution) under nitrogen atmosphere. After stirring for 2 hours, 1,5-dichloropentan-3one (838 mg, 4.580 mmol) was dissolved in diethyl ether (8 mL) and slowly added thereto. -78 ^o After further stirring at C for 4 hours, slowly add 50 mL of ice water and extract with diethyl ether. The organic layer is filtered using anhydrous magnesium sulfate to remove water, and then the solvent is removed under reduced pressure. The remaining product was purified by column (hexane: ethyl acetate = 5: 1) to give 820 mg of the product (yield 65%) ¹ H NMR (CDCl ₃ ): δ 3.52 (t, J = 6.4 Hz, 6H, CH ₂ Cl), 1.80-1.73 (m, 6H, CH ₂ ), 1.56-1.52 (m, 4H, CH ₂ ), 1.42 (s, 4H, CH ₂ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ 73.58, 45.69, 44.95, 38.29, 36.48, 32.94, 26.96, 20.88 ppm.

18 composites

In a nitrogen atmosphere, compound 17 (1.122 g, 4.070 mmol), olso cresol (3.521 g, 32.56 mmol) and aluminum trichloride (0.597 g, 4.477 mmol) were added to a round flask and stirred overnight. Then, add 20 mL diethyl ether and 20 mL water, extract only the organic layer (3 times), remove water with anhydrous magnesium sulfate, and remove the solvent under reduced pressure. The resulting product was purified by column (hexane: ethyl acetate = 10: 1) to give 907 mg of the product. (Yield 61%) IR (KBr): 3535 (OH) cm ^-1 . ¹ H NMR (CDCl ₃ ): δ 7.02 (d, J = 2.0 Hz, 1H, mH), 6.99 (dd, J = 8.8 Hz, 2.0 Hz, 1H, mH), 6.73 (d, J = 8.0 Hz, 1H, oH), 4.67 (s, 1H, OH), 3.53-3.46 (m, 6H, CH ₂ Cl), 2.27 (s, 3H, CH ₃ ), 1.79-1.44 (m, 6H, CH ₂ ), 1.67 -1.62 (m, 2H, CH ₂ ), 1.58-1.53 (m, 4H, CH ₂ ), 1.28-1.20 (br, 2H, CH ₂ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ 151.81, 137.96, 128.89, 124.87, 114.70, 60.83, 46.05, 45.04, 42.09, 36.69, 35.07, 27.26, 21.40, 21.02, 16.54, 14.49 ppm. HRMS (FAB): m / z calcd (M ⁺ C ₁₈ H ₂₇ Cl ₃ O) 364.1131, found 365.1206

19 Synthesis

Into the flask was added compound 18 (907 mg, 2.48 mmol), paraformaldehyde (298 mg, 9.920 mmol), magnesium dichloride (944 mg, 9.92 mmol) and triethyl amine (1.051 g, 10.42 mmol), followed by tetrahydrofuran ( 50 mL). Reflux for 5 hours in a nitrogen atmosphere. After lowering the temperature to room temperature, 50 mL of methylene chloride and 50 mL of water are added thereto, and only the organic layer is extracted. Anhydrous magnesium sulfate was added to the organic layer to remove water, and the solvent was removed under reduced pressure. The resulting product was purified through a column (hexane: ethyl acetate = 20: 1) to give 540 mg of the product. (Yield 58%) IR (KBr): 2947 (OH), 1650 (C = O) cm ^-1 . ¹ H NMR (CDCl ₃ ): δ 11.05 (s, 1H, OH), 9.78 (s, 1H, CH = O), 7.25 (s. 1H, mH), 7.19 (s, 1H, mH), 3.44-3.39 (m, 6H, CH ₂ Cl), 2.19 (s, 3H, CH ₃ ), 1.74-1.43 (m, 12H, CH ₂ ), 1.20-1.11 (br, 2H, CH ₂ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ 196.79, 158.07, 136.98, 135.85, 128.95, 126.85, 119.52, 45.77, 44.88, 42.12, 36.50, 34.64, 33.09, 27.07, 20.85, 15.71 ppm. HRMS (FAB): m / z calcd (M ⁺ C ₁₉ H ₂₇ Cl ₃ O) 393.1151, found 393.1155

20 composites

Compound 19 (520 mg, 1.304 mmol) and sodium iodide (2.932 g, 19.56 mmol) were added to the flask, and 2 mL of acetonitrile was added to reflux for 12 hours. Thereafter, the solvent was removed under reduced pressure, 5 ml of methylene chloride and 5 ml of water were added thereto, and only the organic layer was extracted. The water in the organic layer is removed with anhydrous magnesium sulfate and darkened to remove the solvent. The result was purified through a column (hexane: ethyl acetate = 20: 1) to give 759 mg of the product. (Yield 87%) IR (KBr): 2936 (OH), 1648 (C = O) cm ^-1 . ¹ H NMR (CDCl ₃ ): δ 11.06 (s, 1H, OH), 9.80 (s, 1H, CH = O), 7.25 (s. 1H, mH), 7.17 (d, J = 2.8 Hz, 1H, mH ), 3.21-3.14 (m, 6H, CH ₂ Cl), 2.27 (s, 3H, CH ₃ ), 1.79-1.53 (m, 12H, CH ₂ ), 1.28-1.19 (br, 2H, CH ₂ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ 196.81, 158.20, 137.00, 135.90, 128.90, 126.98, 119.54, 42.17, 38.45, 36.11, 33.93, 27.83, 24.50, 15.84, 7.96, 7.14 ppm.

Synthesis of 21

Compound 20 (680 mg, 1.018 mmol) and cyclohexyl diamine (58 mg, 0.509 mmol) are dissolved in 5 mL of methylene chloride and stirred for 12 hours. Thereafter, the mixture was briefly purified by column using only methylene chloride to obtain a pure yellow solid (560 mg). (Yield 78%) IR (KBr): 2933 (OH), 1629 (C = N) cm ^-1 . ¹ H NMR (CDCl ₃ ): δ 13.45 (s, 2H, OH), 8.34 (s, 2H, CH = N), 7.05 (s, 2H, mH), 6.941 (d, J = 1.6 Hz, 2H, mH ), 3.39-3.36 (m, 2H, cyclohexyl-CH), 3.17-3.09 (m, 12H, CH ₂ I), 2.26 (s, 6H, CH ₃ ), 1.96-1.89 (m, 4H, cyclohexyl-CH ₂ ), .96-1.43 (m, 32H, cyclohexyl-CH ₂ and CH ₂ ), 1.18-1.20 (br, 4H, CH ₂ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ 164.97, 157.2, 135.58, 131.25, 127.12, 125.50, 117.65, 72.89, 42.00, 38.71, 36.14, 34. 18, 33.73, 27.91, 24.57, 24.50, 16.32, 8.26, 7.18 ppm.

22 composite

Compound 21 (364 mg, 0.257 mmol) was added to the flask, dissolved in 5 mL of acetonitrile, and tributyl amine (291 mg, 1.57 mmol) was added thereto. Stir at reflux for two days in a nitrogen atmosphere. Lower the temperature to room temperature, remove the solvent under reduced pressure, add 10 mL of diethyl ether to the remaining solid, stir for 10 minutes, stop the stirring, settle the solid, and remove only the diethyl ether with a pipette. This process was repeated two more times and only the yellow solids were collected to completely remove the solvent under reduced pressure to give 579 mg of the product. (Yield 89%) IR (KBr): 2959 (OH), 1627 (C = N) cm ^-1 . ¹ H NMR (CDCl ₃ ): δ. 13.46 (s, 2H, OH), 8.58 (s, 2H, CH = N), 7.18 (s, 2H, mH), 7.07 (s, 2H, mH), 3.42 (br, 2H, cyclohexyl-CH), 3.32 (br, 16H, NCH ₂ ), 3.16 (br, 32H, NCH ₂ ), 2.10 (s, 6H, CH ₃ ), 1.74-1.20 (br, 108H, cyclohexyl-CH ₂ , CH ₂ ), 0.86 (t, 18H, CH ₃ ), 0.75 (t, 36H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ 164.78, 157.27, 134.04, 130.82, 127.22, 125.15, 117.46, 71.01, 9.96, 59.63, 59.00, 58.86, 53.52, 43.03, 34.89, 33.90, 33.68, 24.16, 24.05, 23.07, 22.78, 20.69, 19.68, 19.53, 17.64, 15.79, 13.58 ppm.

Synthesis of 23

Compound 22 (455 mg, 0.180 mmol) and silver tetrafluoro borate (211 mg, 1.08 mmol) were added to the flask, 12 mL of methylene chloride was added to the solvent, the flask was wrapped with aluminum foil, and stirred at room temperature for one day. Thereafter, the solid was removed by filtration using a glass filter, and the remaining solution was dried under reduced pressure, and then dried under methylene chloride: ethanol = 5: 1 to give 322 mg of a yellow product. (Yield 78%) IR (KBr): 2961 (OH) , 1628 (C = N) cm ⁻¹ . ¹ H NMR (CDCl ₃ ): δ. 13.64 (s, 2H, OH), 8.52 (s, 2H, CH = N), 7.27 (s, 2H, mH), 7.16 (s, 2H, mH), 3.44 (br, 2H, cyclohexyl-CH), 3.30 -3.10 (br, 48H, NCH ₂ ), 2.24 (s, 6H, CH ₃ ), 1.95-1.29 (br, 108H, cyclohexyl-CH ₂ , CH ₂ ), 0.99 (t, 18H, CH ₃ ), 0.90 ( t, 36H, CH ₃ ) ppm.

9, synthesis

Compound 23 (59 mg, 0.026 mmol) and Co (OAc) ₂ (4.6 mg, 0.026 mmol) were added to the vial in a glove box. Then, 1 mL of ethanol was added and stirred for 12 hours. The solvent was removed under reduced pressure and washed twice with diethyl ether to obtain a red solid. 2, 4- dinitrophenol (5.0 mg, 0.026 mmol) was added thereto, and the mixture was stirred for 3 hours in the presence of oxygen. Then, sodium 2,4-dinitrophenolate (27 mg, 0.13 mmol) was added thereto and stirred for 12 hours. The solid was filtered using celite and the remaining solution was dried under reduced pressure to give 73 mg of a dark red solid. IR (KBr): 2961 (OH), 1607 (C = N) cm ⁻¹ . _{^{1 H NMR (DMSO- d 6,}} 38 o C): δ 8.68 (br, 4H, (NO 2) 2 C 6 H 3 O), δ. 8.05 (br, 4H, (NO ₂ ) ₂ C ₆ H ₃ O), 7.85 (br, 2H, CH = N), 7.30 (br, 4H, mH), 6.76 (br, 4H, (NO ₂ ) ₂ C ₆ H ₃ O), 3.58 (br, 2H, cyclohexyl-CH), 3.09 (br, 48H, NCH ₂ ), 2.63 (s, 6H, CH ₃ ), 1.53-1.06 (br, 108H, cyclohexyl-CH _2, CH ₂ ), 0.93-0.85 (m, 54H, CH ₃ ) ppm.

[ Example  6] Synthesis of Complex 10

 It synthesized according to the following scheme 6.

Scheme 6

24 composites

Dissolve 1,7-dichloroheptan-4-one (17.40 g, 95.04 mmol) in diethyl ether (285 mL) under a nitrogen atmosphere. After the temperature was lowered to −78 ° C., a 1.5 M diethyl ether MeLi solution (80.97 g, 142.56 mmol) was slowly added dropwise with a syringe under a nitrogen atmosphere. After stirring at −78 ° C. for 2 hours, water (170 mL) is added to terminate the reaction. Extract three times with diethyl ether (300 mL) to collect only the organic layer. Water was removed with anhydrous magnesium sulfate, filtered and the solvent was removed using a rotary vacuum concentrator to obtain a reaction product. The yield is 17.99 g (95%) and the product obtained can be used for the next reaction without further purification. ¹ H NMR (CDCl ₃ ): δ.3.59 (t, J = 6.4 Hz, 4H, CH ₂ Cl), 1.90-1.86 (m, 4H, CH ₂ ), 1.64-1.60 (m, 4H, CH ₂ ), 1.23 (s, 3H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ.72.32, 45.88, 39.51, 27.60, 27.23 ppm.

25 composites

Under nitrogen atmosphere, ortho-cresol (78.17 g, 722.82 mmol), compound 24 (17.99 g, 90.35 mmol), AlCl ₃ (13.25 g, 99.39 mmol) are mixed in a round bottom flask and stirred overnight. Diethyl ether (500 mL) and water (300 mL) were added to terminate the reaction. The organic layer was received, and the water layer was extracted three more times with diethyl ether (300 mL) to collect the organic layers. Water is removed with anhydrous magnesium sulfate, filtered and the solvent is removed using a rotary vacuum concentrator. The obtained compound was vacuum reduced (2 mmHg) in an 85 degreeC oil bath, and the ortho-cresol thrown in in excess was removed. The compound remaining in the flask was pure enough to be used for the next reaction without further purification and the yield was 25.40 g (97%). ¹ H NMR (CDCl ₃ ): δ.7.01 (d, J = 2.0 Hz, 1H, mH), 6.97 (dd, J = 8.0 Hz, 2.0 Hz, 1H, mH), 6.72 (d, J = 8.0 Hz, 1H, oH), 4.85 (s, 1H, OH), 3.45 (t, J = 6.4 Hz, 4H, CH ₂ Cl), 2.27 (s, 3H, CH ₃ ), 1.86-1.44 (m, 8H, CH ₂ ), 1.30 (s, 3H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ 151.79, 138.67, 129.06, 125.02, 123.45, 114.85, 46.20, 41.12, 39.95, 28.09, 24.22, 16.58 ppm.

26 composites

Compound 25 (25.40 g, 87.83 mmol) is dissolved in tetrahydrofuran (650 mL) under a nitrogen atmosphere. Paraformaldehyde (10.55 g, 351.32 mmol), magnesium chloride (33.52 g, 351.32 mmol) and triethylamine (37.31 g, 368.89 mmol) were added to the flask in order under a nitrogen atmosphere, and the reflux condenser was connected for 5 hours. Stir at reflux. The solvent is removed using a rotary vacuum concentrator and then methylene chloride (500 mL) and water (300 mL) are added. Filtration with celite removes the suspended solids to obtain a methylene chloride layer. The water layer is extracted three more times with 300 mL of methylene chloride and all organic layers are collected. Water was removed with anhydrous magnesium sulfate, filtered and the solvent was removed using a rotary vacuum concentrator to obtain an oily compound. The vacuum pump is used to remove some of the remaining triethylamine. NMR analysis of the obtained compound showed a high purity, which was used without further purification in the next reaction. Yield 26.75 g (96%). ¹ H NMR (CDCl ₃ ): δ.11.14 (s, 1H, OH), 9.87 (s, 1H, CH═O), 7.33 (d, J = 2.4 Hz, 1H, mH), 7.26 (d, J = 2.4 Hz, 1H, mH), 3.47 (t, J = 6.4 Hz, 4H, CH ₂ Cl), 2.30 (s, 3H, CH ₃ ), 1.90-1.40 (m, 8H, CH ₂ ), 1.35 (s, 3H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ.196.87, 158.22, 137.56, 136.11, 128.91, 119.69, 45.88, 40.67, 39.98, 27.96, 24.06, 15.81 ppm.

Synthesis of 27

Compound 26 (26.75 g, 84.32 mmol) is dissolved in acetonitrile (107 mL). Sodium iodide (126.39 g, 843.18 mmol) was added thereto, followed by a reflux condenser, refluxed and stirred overnight. After cooling to room temperature, 300 mL of water are added. Extract three times with diethyl ether (300 mL) to collect only the organic layer. Anhydrous magnesium sulfate was added to remove water from the organic layer, followed by filtration and removal of the solvent using a rotary vacuum concentrator. Pure compound was obtained by silica gel column chromatography using hexane-toluene mixture (5: 1) as a developing solution (22.17 g, 83%). ¹ H NMR (CDCl ₃ ): δ.11.14 (s, 1H, OH), 9.87 (s, 1H, CH = O), 7.33 (d, J = 2.4 Hz, 1H, mH), 7.25 (d, J = 2.4 Hz, 1H, mH), 3.14-3.09 (m, 4H, CH ₂ I), 2.30 (s, 3H, CH ₃ ), 1.87-1.43 (m, 8H, CH ₂ ), 1.34 (s, 3H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ.196.85, 158.20, 137.50, 136.09, 128.85, 126.93, 119.62, 44.28, 39.95, 28.66, 24.16, 15.81, 7.99 ppm.

28 Synthesis

Compound 27 (8.56 g, 17.01 mmol) is dissolved in methylene chloride (97 mL) under a nitrogen atmosphere. Add (±) trans-1,2-diaminocyclohexane (0.97 g, 8.50 mmol) and stir overnight. Removal of the solvent under reduced pressure gives a pure compound. (9.00 g, 98%). ¹ H NMR (CDCl ₃ ): δ.13.48 (s, 1H, OH), 8.31 (s, 1H, CH = N), 7.04 (d, J = 1.6 Hz, 1H, mH), 6.91 (d, J = 1.6 Hz, 1H, mH), 3.38-3.35 (m, 1H, cyclohexyl-CH), 3.08-3.03 (m, 4H, CH ₂ I), 2.25 (s, 3H, CH ₃ ), 1.96-1.89 (m, 2H, cyclohexyl-CH ₂ ), 1.96-1.43 (m, 10H, cyclohexyl-CH ₂ and CH ₂ ), 1.26 (s, 3H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ.165.01, 157.31, 136.12, 131.35, 126.93, 125.54, 117.67, 72.94, 44.47, 39.79, 33.73, 28.72, 24.57, 24.32, 16.28, 8.38, 8.26 ppm.

29 composites

Dissolve compound 28 (0.855 g, 0.79 mmol) in acetonitrile (8.5 mL) under nitrogen atmosphere, add tributylamine (1.17 g, 6.32 mmol), and connect the reflux condenser. After stirring for 48 hours at reflux, the solvent is removed by a rotary vacuum distillation apparatus. Diethyl ether (20 mL) was added and stirred for 15 minutes to precipitate a solid substance. The solution was then decanted to remove only a solid compound. This process is repeated twice more to give a pale off-white solid compound. The obtained solid compound was added to AgBF ₄ (0.642 g, 3.30 mmol) and ethanol solution (40 mL) were added slowly while stirring. After stirring for 24 hours in a light-blocked atmosphere, the resulting AgI was removed by filtration using celite. The solvent was removed under reduced pressure in vacuo and then dissolved in methylene chloride (6 mL) and filtered again using celite to remove suspended solids. Pure compound was obtained through silica gel column chromatography using methylene chloride-ethanol mixture (5: 1), from which the solvent was removed, as a developing solution (1.23 g, 90%). ¹ H NMR (CDCl ₃ ): δ. 13.55 (s, 1H, OH), 8.42 (s, 1H, CH = N), 7.12 (s, 1H, mH), 7.08 (s, 1H, mH), 3.38 ( br, 1H, cyclohexyl-CH), 3.06 (br, 16H, NCH ₂ ), 2.20 (s, 3H, CH ₃ ), 1.88-1.84 (br, 2H, cyclohexyl-CH ₂ ), 1.68-1.26 (br, 36H ), 0.87-0.86 (br, 18H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (CDCl ₃ ): δ.165.23, 157.79, 135.21, 131.17, 127.18, 125.76, 117.91, 72.05, 59.16, 58.63, 40.16, 38.10, 37.71, 26.45, 24.91, 23.90, 20.31, 19.80, 17.30, 16.01, 13.97, 13.80, 13.79 ppm.

10 composite

Compound 29 (100 mg, 0.06 mmol) and Co (OAc) ₂ (10.7 mg, 0.06 mmol) were added to the flask and dissolved by addition of ethanol (3 mL). After stirring for 3 hours at room temperature, the solvent is removed under reduced pressure. Diethyl ether (2 mL) was added and the mixture was stirred for 15 minutes, followed by precipitation of the solid material to remove the supernatant. The solvent was completely removed by distillation under vacuum, and methylene chloride (3 mL) was added to dissolve. 2,4-Dinitrophenol (11.1 mg, 0.06 mmol) was added thereto, and the mixture was stirred under an oxygen atmosphere for 3 hours. Sodium-2,4-dinitrophenolate (74.5 mg, 0.30 mmol) was added under oxygen atmosphere and stirred overnight. Filtration with Celite and vacuum removal of solvent gave compound (137 mg, 100%). ¹ H NMR (dmso-d ₆ , 38 ° C): δ. 8.65 (br, 2H, (NO ₂ ) ₂ C ₆ H ₃ O), δ.7.88 (br, 3H, (NO ₂ ) ₂ C ₆ H ₃ O, CH = N), 7.31 (br, 2H, mH) , 6.39 (br, 2H, (NO ₂ ) ₂ C ₆ H ₃ O), 3.38 (br, 1H, cyclohexyl-CH), 3.08 (br, 16H, NCH ₂ ), 2.64 (s, 3H, CH ₃ ), 2.06-1.85 (br, 2H, cyclohexyl-CH ₂ ), 1.50-1.15 (br, 36H), 0.86 (br, 18H, CH ₃ ) ppm.

Example 7 Synthesis of Complex Compound 11

3-methyl ^{_{-5 - [{BF 4 - Bu}} 3 N + (CH 2) 3} 2 CH 3 C}] - salicylaldehyde compound (493 mg, 0.623 mmol) and 2,3-diamino -2,3 Dimethylbutane (36 mg, 0.311 mmol) was added to the flask, 4 mL of ethanol and 180 mg of molecular sieve were added and refluxed under nitrogen for 12 hours. The mixture was filtered through celite to remove molecular sieves, and the solvent was removed under reduced pressure to obtain a yellow solid. Add Co (OAc) ₂ (55 mg, 0.31 mmol) and dissolve in 10 mL of ethanol and stir at room temperature for 5 hours. The reaction mixture was then depressurized to remove ethanol, washed twice with diethyl ether, 2,4-dinitrophenol (57 mg, 0.311 mmol) was added, dissolved in 10 mL of methylene chloride, and stirred for 12 hours in the presence of oxygen. Sodium-2,4-dinitrophenolate (320 mg, 1.56 mmol) was added thereto, stirred for 12 hours, and then filtered through celite to remove the solution under reduced pressure to obtain 736 mg of a dark red solid. ¹ H NMR (dmso-d _6, 38 ° C.): δ 8.62 (br, 4H, (NO ₂ ) ₂ C ₆ H ₃ O), 7.87 (br, 4H, (NO ₂ ) ₂ C ₆ H ₃ O), 7.72 (br, 2H, CH = N), 7.50 (br, 2H, m -H), 7.35 (br, 2H, m -H), 6.47 (br, 4H, (NO ₂ ) ₂ C ₆ H ₃ O) , 3.11 (br, 32H, NCH ₂ ), 2.70 (s, 6H, CH ₃ ), 1.66-1.22 (br, 82H), 0.88 (br, 36H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (dmso-d ₆ ): δ 164.67, 159.42, 132.30, 129.71, 128.86 (br), 128.46 (br), 127.42 (br), 124.05 (br), 118.84, 73.92, 57.74, 57.19 , 25.94, 23.33, 22.61, 21.05, 18.73, 16.68, 16.43, 12.93 ppm.

[ Example  8] Synthesis of Complex 12

3-methyl ^{_{-5 - [{BF 4 - Bu}} 3 N + (CH 2) 3} 2 CH}] - salicylaldehyde salen ligand (500 mg, 0.301 mmol) and Co (OAc) made from a compound ₂ (53 mg , 0.30 mmol) was added to the flask and dissolved in 15 mL of ethanol, followed by stirring for 3 hours in a nitrogen atmosphere. The solvent was removed under reduced pressure, washed twice with diethyl ether, dissolved in 10 mL of methylene chloride, and then HBF ₄ (49 mg, 0.30 mmol) was added and stirred for 3 hours in the presence of oxygen. Then, the solvent was removed under reduced pressure to obtain 520 mg of pure compound. Synthesis was carried out according to the method previously known by the inventor ( Angew . Chem . Int . Ed . , 2008 , 47 , 7306).

Example 9 Synthesis of Complex Compound 13

3-t- butyl ^{_{-5 - [{BF 4 - Bu}} 3 N + (CH 2) 3} 2 CH}] - salicylaldehyde using the salen ligand made from the compound made in the same way as complex 12. ¹ H NMR (dmso-d _6, 40 ° C): δ 7.68 (s, 1H, CH = N), 7.36 (s, 1H, m -H), 7.23 (s, 1H, m -H), 3.61 (br , 1H, NCH), 3.31-2.91 (br, 16H, NCH ₂ ), 2.04 (br, 1H, cyclohexyl-CH ₂ ), 1.89 (br, 1H, cyclohexyl-CH ₂ ), 1.74 (s, 9H, C ( CH ₃ ) ₃ ), 1.68-1.35 (br, 20H, CH ₂ ), 1.32-1.18 (br, 12H, CH ₂ ), 0.91 (t, J = 7.2 Hz, 18H, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (dmso-d ₆ ): δ 161.66, 160.42, 140.90, 129.71, 128.38, 127.31, 117.38, 67.40, 55.85, 33.89, 31.11, 28.70, 27.70 (br), 22.58, 21.29, 19.47, 17.45, 15.21, 11.69 ppm.

[ Example  10] Synthesis of Complex 14

Compound 10 was dissolved in propylene oxide, left for one hour, and then vacuum reduced. ¹ H NMR (dmso-d ₆ ): δ 8.59 (s, 1H, (NO ₂ ) ₂ C ₆ H ₃ O), 8.42 (s, 1H, spiro-Meisenheimer anion), 7.74 (s, 1H, (NO ₂₎ ) ₂ C ₆ H ₃ O), 7.39-6.98 (m, 3H, mH, CH = N), 6.81 (s, 1H, spiro-Meisenheimer anion), 6.29 (s, (NO ₂ ) ₂ C ₆ H ₃ O ), 5.35 (s, 1H, spiro-Meisenheimer anion), 4.43-4.29 (m, 1H, spiro-Meisenheimer anion), 4.21-3.99 (m, 2H, spiro-Meisenheimer anion), 3.21 (br, 1H, NCH) , 3.09 (br, 16H, NCH ₂ ), 2.93 (m, 3H, spiro-Meisenheimer anion), 2.62 (s, 3H, CH ₃ ), 1.98 (br, 1H, cyclohexyl-CH ₂ ), 1.62-1.39 (br , 20H, CH ₂ ), 1.39-1.15 (br, 15H, CH ₂ , CH ₃ ), 0.91 (br, 18H, CH ₃ ) ppm.

[ Example  11] Structural Analysis of Complexes

In-depth structural analysis was performed on the complexes 7 and 8 prepared in Examples 3 and 4.

(1) ¹ H, ¹³ C and ¹⁵ N NMR spectra and IR spectra

1, 2, 3, 4, and 5 are dmso-d ₆ of 7 and 8 , respectively. ¹ H NMR spectrum, ¹³ C NMR spectrum, ¹³ N NMR spectrum, THF-d ₈ and CD ₂ Cl ₂ in solvent A ¹ H NMR spectrum, and an IR spectrum, in the solvent are compared and shown. It is clear that the two compounds exhibit completely different behavior. In the case of complex 8 prepared with a ligand of which R is t-butyl, the signal was sharp in both ¹ H and ¹³ C NMR spectra, indicating a typical aspect of the tetradentate Salen-Co (III) compound. ^{In the 15} N NMR spectrum, only one signal was observed at -163.43 ppm regardless of temperature.

For ¹ H and ¹³ C NMR spectra of complex 7 prepared with a ligand of R is methyl (Example 3), a fairly complex and broad signal was obtained at room temperature, and a simple but broad signal was obtained at 40 ° C. At 80 ° C., a sharp signal was obtained. The ratio of [DNP] / [Salen-unit] obtained from the integration of the ¹ H NMR spectrum is close to 4.0 rather than 5.0 observed at 8 . ^{In the 15} N NMR spectrum, two signals were observed at -156.32 and -159.21 ppm at room temperature, one broad signal was found at 40 ° C, and only one sharp signal at 80 ° C.

7 from THF-d ₈ or CD ₂ Cl ₂ The ¹ H NMR spectral behavior of 8 is also quite different (Fig. 4). The ¹ H NMR spectrum of 8 shows a set of Salen-unit signals and the DNP signal is quite broad. And the peculiar thing is that a little signal is observed at the abnormal site -2 ~ 0 ppm, suggesting that some paramagnetic compound is present. 7 of ^{The 1} H NMR spectrum also showed only one set of Salen-unit signals, but its chemical shift value was significantly different from that of 8 . DNP signals were observed broadly at 7.88, 8.01, and 8.59 ppm. Strangely, only two of the four DNPs observed at dmso-d ₆ were found with an integration ratio of [DNP] / [Salen-unit] of about 2.0. Two were not observed. The ¹ H NMR spectral behavior of 7 and 8 measured in CD ₂ Cl ₂ is similar to that observed in THF-d ₈ .

In the ¹⁵ N NMR spectrum obtained from THF-d ₈ , the signal is sharply observed at -166.80 ppm and in the case of 7 at -154.32 ppm. The difference of 12.5 ppm of the chemical shift value of the signals of the two compounds cannot be considered simply a difference due to the substituent effect. The chemical shift value of ¹⁵ N NMR in the imine ( -N = CC ₄ H ₄ -X) and the hydrazone (N- N = CC ₄ H ₄ -X) compounds was approximately 10 gradients in the Hammett-type equation. Has been reported. Considering the substituent values of methyl and tertiary-butyl, the difference in the chemical shift values between the two substituents is 1 ppm or less (Neuvonen, K .; F, F .; Neuvonen, H .; Koch, A .; Kleinpeter , E .; Pihlaja, K. J. Org . Chem . 2003 , 68 , 2151.). In the case of dipyrrolmethene ligand and zinc (II) compound produced therein, the difference of ⁵ N NMR chemical shift value was 2 ppm when hydrogen was substituted with ethyl (Wood, TE; Berno, B .; Beshara, CS; Thompson , Alison, J. Org . Chem . 2006 , 71 , 2964.). In fact, the difference in chemical shift values is small at 2.86 ppm in the ligand stage used to synthesize 7 and 8 . Therefore, the observed Chem mikeol shift 12.5 ppm can be concluded that due to the structure that has a different respectively 7 and 8, the two compounds. Changing the temperature at THF-d ₈ ¹⁵ In the case of 7, when observing the N NMR signal is quite broad haejyeoseo at ^{-75 o C full width at half maximum} (FWHM) value of 10 ppm by reducing the temperature was for an 8 by a relatively sharp to -75 ^o FWHM at C was 1.5 ppm. The results suggest that 8 has a conventional Salen-Co (III) compound structure in which all four ligands of Salen are doubled, while others have a more flexible structure.

As shown in FIG. 5, signals of the 1200-1400 cm ⁻¹ portion corresponding to the —NO ₂ symmetric oscillation of the IR spectrum of the two compounds are completely different from each other.

(2) compound structure proposal

The ¹ H, ^{1 3} C, and ¹⁵ N NMR spectra of the eight compounds described above are not unreasonable to interpret as compound structures made of conventional Salen ligands, in which all four ligands of Salen are cobalt-coated. ICP-AES, elemental analysis and ¹⁹ F NMR analysis showed that 1 equivalent of NaBF ₄ was trapped in the compound. DNP signals are broadly observed in the ¹ H NMR spectrum, indicating that the DNP ligand is in and out of coordination. As part of this flow, there is a possibility of brief presence of a 5-coordinate-pyramidal compound, and a 5-coordinate-pyramidal cobalt compound is known as a paramagnetic compound ((a) Konig, E .; Kremer, S. Schnakig, R., Kanellakopulos, B. Chem . Phys . 1978 , 34 , 79. (b) Kemper, S .; Hrob, P .; Kaupp, M .; Schl, NE J. Am . Chem . Soc . 2009, 131, 4172.) As a result, an abnormal signal is observed at all times -2 ~ 0 ppm part of the ¹ H NMR spectrum for compound 8.

In the case of compound 7 , the analytical data can be explained on the assumption that the imine is not coordinated, and the structure was proved through the following DFT calculation and electrochemical experiment. Instead of imine coordination, it is characterized by four DNP covalent ions of the quaternary ammonium salt. As shown in the above scheme, the final step of the catalyst synthesis is the reaction of 5 equivalents of NaDNP suspended in CH ₂ Cl ₂ to exchange [BF ₄ ] ⁻ for DNP anions. The ratio of the integral values of [DNP] / [Salen-unit] is 4.0 and it also does not change significantly with more NaDNP (10 equivalents) or with longer reaction times. Ie 4 BF ₄ One of them remains unsubstituted. BF ₄ in ¹⁹ F NMR Spectrum Signals were observed but, unlike in 8 , BF ₄ from the fact that no Na ⁺ ions were observed in the ICP-AES assay. It can be seen that the anion is present as a counterion of the quaternary ammonium salt. Even when the catalyst was prepared with a ligand having more quaternary ammonium salt units, such as compound 9 , a compound containing only 4 DNPs was obtained even with a considerable excess of NaDNP and a long time. Perhaps a coordination compound with an octahedral structure co-ordinated by two Salen-phenoxy ligands and four DNPs in a methylene chloride solvent is obtained, and the formation of these compounds induces an anion exchange reaction. Cobalt trivalent metals are classified as hard-acids, and strong acids favor DNP over soft imine-based compounds, suggesting that this heterogeneous compound is obtained. In the case of compound 8 , tert-butyl steric hindrance prevents the formation of compounds of this structure. There are known examples of octahedral cobalt (III) compounds in which cobalt has a −3 charge ((a) Yagi, T .; Hanai, H .; Komorita, T .; Suzuki T .; Kaizaki S. J. Chem . Soc ., Dalton Trans . 2002 , 1126. (b) Fujita, M .; Gillards, RD Polyhedron 1988, 7 , 2731.)

The ¹ H and ¹³ C NMR spectra and IR spectral behavior of the 5, 9, and 10 compounds are similar to the behavior observed in the spectra of the 7 compounds and can be designated as compounds having a different coordination pattern without imine coordination. In particular, in the case of 5 compounds, the patents previously disclosed by the inventors ( Angew . Chem . Int . Ed . , 2008 , accepted) and the patents filed [Korean Patent Application No. 10-2008-0015454 (filed Feb. 20, 2008) NAME OF THE INVENTION: process for recovering catalyst from copolymer production process); Cleavage, Sujith S, Eun-Kyoung Noh, Min-Kee Min, "A process producing polycabonate and a coordination complexes used there for" PCT / KR2008 / 002453 (April 30, 2008); Sujith S, Jae Ki Min, Jong Eon Seong, Sung Jea Na, and Bun Yeoul Lee * "A Highly Active and Recyclable Catalytic System for CO ₂ / (Propylene Oxide)" has been interpreted as a conventional Salen-compound assigned by imine, such as the structure of 8 , but through the present invention the structure Correct it with

The ¹ H and ¹³ C NMR spectra and IR spectral behavior of Compounds 6 and 11 are similar to those observed in the spectra of 8 compounds and can be assigned to the structure of a typical Salen-compound assigned by imine.

(3) DFT calculation

Immigration this conventional imine structure and the seven compounds of non-coordinating different coordinate form and in isomeric relation coordination and two DNP is coordinated to two axial site and the remaining two DNP is the compound of structure present in a free state DFT calculations were performed to see the energy levels. 6 shows the most stable conformation of the 7 structures obtained in the calculations. The results are 132 Kcal / mol more stable than in a different coordination structure of the energy levels of the compound 7 a conventional structure in which migration times for the form claimed in the present invention. This energy level difference is significant.

(4) fluidity of DNP ligand

The ¹ H NMR in methylene chloride used for the anion exchange reaction, the final step in the preparation of the catalyst, shows that for compounds 7 , 9 and 10 the DNP signal is [DNP] / [Salen-unit] integrated at 8.4, 8.1, and 7.9 ppm. Observed with 2.0 (FIG. 4). That is, only two of the four DNPs are observed and two are not observed because the two DNPs are in and out of coordination and decoordination states at the NMR time level. On the other hand, in case of 5 compound, all 4 DNP signals were observed in the same region. The chemical shift value of the observed DNP signal is completely different from the chemical shift value of [Bu ₄ N] ⁺ [DNP] ⁻ , and the observed signal may be attributed to the coordinated DNP. That is, 7 , 9 , and 10 compounds are in a state in which two DNPs are coordinated at room temperature in a methylene chloride solvent, and the other two are in and out of coordinating and decoordinating states. In the case of compound 5 , all four DNPs are in a coordinated state. 7 is a diagram showing the state of the DNP at room temperature depending on the solvent for a compound having a different structure that is not coordinated imine. These results demonstrate that the structure of the compound obtained in the last anion reaction is correct for the claim that the Salen-phenoxy and the four DNPs are coordinated, and the structure adopted in the DFT calculation.

The ¹ H NMR spectrum of 7 measured at room temperature in THF-d ₈ shows only two DNPs coordinated at 8.6, 8.1 and 7.9 ppm as in methylene chloride (FIG. 4). Lowering the temperature to 0 ° C sharpens the observed signal to reveal the coupling behavior. ^The coordinated DNP signal can be clearly interpreted by measuring the ¹ H- ¹ H COSY NMR spectrum (FIG. 8). Lowering the temperature to -25 ^o C further observed a new DNP signal (* signal in FIG. 8). The chemical shift value of this new signal is similar to the chemical shift value of [Bu ₄ N] ⁺ DNP ^- and can be interpreted as a DNP that stays in a decoordinated state for a long time. At 70 ° C., all four DNPs were observed in a broad set at 9.3, 9.0, and 7.8 ppm. This is similar to the coordinated DNP signal chemical shift, which means that all four DNPs stay in the coordinated state for a long time. In other words, as the temperature increases, on average, DNP is closer to the cobalt center. Around the decoordinated DNP, the solvent is enclosed to stabilize, which is a reaction with reduced entropy. As such, the decoordination reaction with reduced entropy is advantageous at low temperatures, so that the signal is decoordinated by lowering the temperature and, on the contrary, transitioned to the coordinated state at a high temperature. Equilibrium transitions from contact ion pairs to solvent separated ion pairs by lowering the temperature, a similar phenomenon, are well known ((a) Streitwieser Jr., A .; Chang, CJ; Hollyhead, WB; Murdoch, JR J. Am . Chem Soc 1972, 94, 5288. (b) Hogen- Esch, TE;..... Smid, J. J. Am Chem Soc 1966, 88, 307. (c) L, J.-M .; Rosokha , SV; Lindeman, SV; Neretin, IS; Kochi, JK J. Am . Chem . Soc. 2005 , 127 , 1797.) FIG. 8 shows the VT ¹ H NMR spectrum of 7 at THF-d ₈ .

A typical immigration the ¹ H NMR spectrum of behavior as a function of temperature from THF-d ₈ of Salen compound 8 for ship is quite different as observed in the 7. It is also evidence that 7 and 8 have very different structures. By lowering the temperature to 0 ° C, all DNP signals become more broad and cannot be observed at all. At −25 ° C., a relatively sharp set of DNP signals is observed with values of [DNP] / [Salen-unit] integral ratio 2.0 at 8.1, 7.6, and 6.8 ppm. In addition, a fairly broad set of signals are observed at 8.9, 8.0, and 6.8 ppm, whose chemical shift values are the chemical shift values (8.7, 8.0, and 6.8 ppm) of DNP that stay long in the decoordination state observed at 7 . Similar to At -50 ^o C, both sets of signals are sharper, so you can see both sets of DNP signals clearly. The DNP signals observed at 8.1, 7.6, and 6.8 ppm can be designated as two DNPs coordinated to the axial site of a typical Salen coordination compound, while the other set of signals observed at 8.9, 8.0, and 6.8 ppm is decoordinated. Can be specified as a signal in the closed state.

The DNP state was determined by ¹ H NMR at room temperature in THF according to the ligand structure. In case of 7 , only two coordinated DNP signals were observed in one set and the other two were not observed. The two unobserved DNPs suggest that they are in and out of coordination and decoordination states. On the other hand, in case of 5 , 9 , and 10 , one set of two coordinated DNP signals and one set of two DNP signals mainly staying in the decoordinated state are observed. Observed at 9 , 10 The two DNP signals, which mainly stay in the decoordinated state, are considerably broader than those observed at 5 . This suggests that they stay less decoordinated at 9 and 10 than at 5 . In conclusion, the degree of staying in the coordinated state (binding affinity for cobalt) of the two DNPs mainly staying in the decoordinated state is in the order of 7 > 9 and 10 > 5 .

¹ H NMR spectra at 40 ° C. in dmso-d ₆ of 5 , 7 , 9 , and 10 show all four DNPs as a set broad signal (FIG. 1). Its chemical shift values (8.6, 7.8, and 6.4 ppm) are similar to the chemical shift values of [Bu ₄ N] ⁺ DNP ⁻ (8.58, 7.80, 6.35 ppm). Therefore, it can be said that all four DNPs stay at 40 DEG C mainly in a coordinating state. However, since the signal is quite broad, it cannot be ruled out of going back and forth from coordination and decoordination. At room temperature, another set of DNP signals is observed with an integral ratio of 1: 3 with a set of DNP signals predominantly staying in another decoordinated state at 8.5, 8.1, and 7.8 ppm. Since the chemical shift value of the less observed DNP signal is similar to the chemical shift value of the coordinated DNP observed in THF and methylene chloride, it can be designated as coordinated DNP. In other words, at room temperature in DMSO, one DNP stays in a predominantly coordinated state and the other three DNPs stay in a decoordinated state. It is assumed that the DMSO is coordinated in the vacancy generated by decoordination of DNP. DMSO is very well coordinated with strong acids like cobalt trivalent metal.

(5) Complex NMR spectrum analysis observed in dmso-d ₆

The ¹ H, ¹³ C, and ¹⁵ N NMR spectra of the complex 7 observed in dmso-d ₆ can be understood as the different structure and state of the DNP that are not coordinated with the imines presented above. 7 In the structure and state of compound 7 at room temperature in DMSO, the two phenoxy ligands of one Salen-unit are in different situations. One is in trans-position for DMSO and the other is in trans-position for DNP. Therefore, two signals are observed in the ¹⁵ N NMR spectrum (FIG. 3), and some of the aromatic signals in the ¹ H and ³ C NMR spectra are split in a 1: 1 ratio (FIGS. 1 and 2). What is unusual is that the NC H ₂ C H ₂ N signals are split in a 1: 1: 2 ratio at 4.3, 4.15, and 4.1 ppm. ^As a result of ¹ H- ¹ H COSY NMR spectrum analysis, it can be seen that three signals originate from one NC H ₂ C H ₂ N-unit (FIG. 1). In the structure obtained from the DFT calculation, the conformation of = NCH ₂ CH ₂ N = monomer main surface is shown, which is close to the structure shown in FIG. In this structure, the conversion of cobalt octahedron into structural isomers is impossible, so this structure, which is coordinated by three DMSOs and one DNP, is chiral. Due to this chirality, the two hydrogens of NC H ₂ show NMR shifts at different positions. For complexes with chiral centers, such as 5 and 10 complexes, ¹ H and ¹³ C NMR are much more complex. As the temperature is raised to 40 ° C, the two coordinating DNP signals disappear and appear as one broad signal. In this case, the asymmetric coordination environment is broken and a simple Salen-ligand signal appears. In THF and CH ₂ Cl ₂ , the coordinating environment around cobalt is symmetrical at room temperature as shown in FIG. 7, resulting in sharp Salen ligand signals at ¹ H, ¹³ C, and ¹⁵ N NMR.

(6) Cyclic Voltammetric (CV) Experiment

CV experiments indirectly prove that 5 and 6 have very different structures. If 5 and 6 have the same structure, the reduction reaction can be expected to occur more well in compound 5 having methyl as a substituent. This is because methyl donating ability is lower than methyl-butyl-butyl, which causes cobalt centers to be less rich in electrons, making it easier for electrons to enter from electrodes. However, the observed result is the opposite. 5 with a methyl substituent as occurs in potential of more negative than the reduction 6. E _1/2 value of the Co (III / II) was observed 5 and 6 compounds -0.076 and -0.013 V vs. angle for each SCE. The reduction potential difference 63 mV between the two compounds is not small. The reduction potential difference 59mV from the Nernst equation (E = E ^o- (0.0592) log {[Ox] / [Red]}) is 10 times the [Co (II)] / [Co (III)] ratio at the same potential Means that.

On the other hand, compounds 12 and 13, which do not have any DNP ligands, are expected to have the same structure of conventional imine coordination regardless of the tertiary-butyl, methyl attached to the ligand, in solvents without coordination ability, such as methylene chloride. do. Have compounds 12 and 13 In CV studies on methylene chloride, both compounds show the same reduction potential (0.63 Vvs. SCE). That is, in the same structure, there is no reduction potential difference due to the difference between methyl and tertiary-butyl substituents, and the reduction potential difference suggests that the two compounds have different coordination forms. When the solvent was changed from CH ₂ Cl ₂ to DMSO, the reduction potential values were again different and the reduction potential values of 12 and 13 (-0.074 and -0.011 V vs. SCE) observed in DMSO were reduced to 5 and 6 observed in DMSO. Similar to the potential values (-0.076 and -0.013 V vs. SCE). DMSO is a ligand that is well coordinated with cobalt trivalent metals. In DMSO solvents, four DMSOs coordinate to 12 compounds with methyl substituents and transfer to heterogeneous coordination forms such as 5 , which is not imine coordinated.

(7) initiation reaction

Compound 10 reacts with propylene oxide. 9 is a ¹ H NMR spectrum showing the reaction of Compound 10 or 8 with propylene oxide. The signal marked with * is a newly generated signal and is an anion of Meisenheimer's salt shown in the formula ( 14 ). Oxygen of the alkoxide obtained by attacking propylene oxide coordinated by DNP is an anion formed by re-attacking the ipso -position of the benzene ring. Salen's aromatic signal is observed to be quite complex at 7.0 to 7.4 ppm, which is not so observed because of the destruction of the Salen-unit. The addition of acetic acid in excess to the compound obtained by reaction with propylene oxide suggests that only three Salen aromatic signals are observed, suggesting that the Salen-unit was not destroyed. The anion of Meisenheimer's salt stops at a step where the integral ratio of [Meisenheimer's anion] / [DNP] is 1: 1. During the first hour, DNP converts significantly to the anions of Meisenheimer's salt, resulting in an integral ratio of [Meisenheimer's anion] / [DNP] to 1: 1, but after two hours, the integral does not change, so the integral remains unchanged after two hours. . Anions of the Meisenheimer salts are compounds of structures already known long ago (Fendler, EJ; Fendler, JH; Byrne, WE; Griff, CE J. Org . Chem . 1968 , 33 , 4141. (b) Bernasconi, CF; Cross, HS J. Org . Chem . 1974 , 39 , 1054.)

It is observed that the rate at which DNP is converted to the anion of Meisenheimer's salt drops considerably when water is present over a certain amount. In the presence of 5 equivalents of water compared to cobalt, no difference was observed in the rate, but when 50 equivalents of water were added, the rate was significantly reduced, and the integration ratio of [Meisenheimer's anion] / [DNP] was 0.47 after 1 hour, 0.53, After 4 hours, the 14 form of compound was not obtained and the integral ratio remained at 0.63 (FIG. 8).

The reactivity of compound 8 with propylene oxide in a conventional imine coordinated structure differs from that observed for compound 10 in a different coordination mode where imine is not coordinated. Anions of the same Meisenheimer salts are observed, but the integral ratio of [Anions of Meisenheimer salts] / [DNP] does not stop at 1.0 but gradually increases over time (1 hour, 0.96; 2 hours, 1.4; 7 hours). , 1.8; 20 hours, 2.0). In addition, a very different aspect from that observed in 10 shows that a large amount of broad signal is observed between -1 and 0.5 ppm, indicating that a reduction reaction to paramagnetic cobalt (II) compound occurred. This signal increases more and more over time. Cobalt divalent compounds have no catalytic activity.

[ Example  12] CO2 / Propylene oxide  Manufacturing Process Of Copolymerization

In a 50 mL bomb reactor, the complex prepared in Example 3-10 (calculated according to 7.58 monomer / catalyst ratio) and propylene oxide (10.0 g, 172 mmol) were placed in a dry box and the reactor assembled. As soon as the reactor was taken out of the dry box, carbon dioxide was injected at 18 bar pressure and the reactor was immersed in an oil bath previously adjusted to a temperature of 80 ° C. and stirring started. The time at which the carbon dioxide pressure began to drop was measured and recorded. After that time, the reaction was completed for 1 hour and the reaction was terminated by subtracting the carbon dioxide gas pressure. 10 g of the monomer was further added to the obtained viscous solution to lower the viscosity of the solution, and then passed through a silica gel (400 mg, manufactured by Merck, 0.040-0.063 mm particle diameter (230-400 mesh) column to obtain a colorless solution. The monomer was removed under reduced pressure in vacuo to give a white solid, the mass of the resulting polymer was measured to calculate the TON (Turnover Number), and the selectivity was calculated by analyzing the ¹ H NMR spectrum of the obtained polymer. It was obtained by calibrating with polystyrene standard using.

[ Example  13] Recovery Process of Copolymer and Catalyst

In the case of 5 , 7 and 10 compounds, the catalyst was recovered in the following manner. The cobalt catalyst component of the upper part of the silica column of Example 12 was combined and the colored part was collected and dispersed in a methanol solution saturated with NaBF ₄ to obtain a red solution. The red solution was filtered and NaBF ₄ The resulting solution was collected twice by washing with saturated methanol solution until the silica became colorless and the solvent was removed under vacuum reduced pressure. When methylene chloride was added to the obtained solid, the brown cobalt compound was dissolved in methylene chloride and NaBF ₄ was not dissolved as a white solid, which could be separated. To the methylene chloride solution was added 2 equivalents of solid 2,4-dinitrophenol and 4 equivalents of sodium 2,4-dinitrophenolate per mole of catalyst used above, followed by stirring overnight. Filtration gave a methylene chloride solution and the solvent was removed to give a brown powder. Thus recovered compound was confirmed to be the same as the catalytic compound by ¹ H NMR analysis and showed similar activity in the copolymerization reaction.

Table 1 summarizes the polymerization reactivity of each catalyst.

[Table 1] Polymerization Reactivity of Each Catalyst ^a

^a Polymerization conditions: PO (10 g, 170 mmol), [PO] / [Cat] = 100,000, CO ₂ (2.0-1.7 MPa), temperature 70-75 ° C, reaction time 60 minutes. ^b Calculated based on the mass of the polymer, including the cyclic carbonate. ^{c 1} H calculated by NMR. ^d Measured using GPC based on polystyrene. ^e Induction time represents 1 to 10 hours, depending on the batch. ^f Polymerization with 220 g of PO.

Table 1 above shows compounds of conventional structures for immigration, 6 , 8 , And 11 has no polymerization activity or significantly lower activity. On the other hand, compounds 5 , 7 , and 10 having a heterogeneous structure, which are not coordinated by imine, which are a feature of the present invention, can be seen that the polymerization activity is outstanding. Oddly, compound 9 , which had an unusual structure with no imine coordination but included six ammonium units, showed no activity.

The order of activity (TOF) is 5 > 10 > 7 , which is the reverse order of binding affinity for cobalt of weakly binding DNP to and from cobalt.

A significant number of polymerization experiments were conducted with 10 compounds. Severe induction time changes (1 to 12 hours) were observed at high summer and high humidity conditions. After the induction time, the polymerization rate was almost constant (TOF, 9,000 ~ 11,000 h ^-1 ). The amount of water that penetrates into the dry box to assemble the polymerization reactor is not negligible in the summer, and in this case, the polymerization reaction system absorbs the water and the induction time changes according to the amount of water. Indeed, in winter, when the dry and cold temperatures were reduced, the induction time was reduced to 1 hour, with additional water added (50 equivalents to cobalt) increasing the induction time to 3 hours (entry 10). A significant addition of water (250 equiv) resulted in no polymerization at all.

The NMR revealed that the presence of a certain amount of water significantly reduced the initiation reaction rate of DNP attacking propylene oxad (FIG. 9). Once the 15 compound obtained by reacting with propylene oxide was used as a catalyst, it was confirmed that the problem of severely changing the induction time with respect to the amount in water was solved (sequence 13). The use of 15 as a catalyst reduces the sensitivity to water, allowing polymerization to be achieved even at a [propylene oxide] / [catalyst] ratio of 150000: 1, further improving TON (entry 14). Under these conditions, the 10 compound showed no polymerization activity at all, even though the propylene oxide was well purified. 15 compound is obtained by dissolving compound 10 in propylene oxide steaming for 1 hour. Under these synthesis reaction conditions, the ratio of [water remaining in propylene oxide] / [compound 10 ] can be ignored.

1 shows dmso-d ₆ of 7 and 8 Show ¹ H NMR spectrum in solvent. The signal labeled X is the DNP signal, and the 2D spectrum in the box is the ¹ H- ¹ H COSY NMR spectrum obtained at 20 ^o T of 7.

2 shows dmso-d ₆ of 7 and 8 Show ¹³ C NMR spectrum in solvent.

3 shows dmso-d ₆ of 7 and 8 Show ¹³ N NMR spectrum in solvent.

4 shows THF-d ₈ and CD ₂ Cl ₂ of 7 and 8 ; Show ¹ H NMR spectrum in solvent.

5 shows the IR spectra of 7 and 8 .

6 shows the most stable conformation of the 7 structures obtained in the DFT calculation. For simplicity only the coordinated oxygen in the DNP ligand was included in the diagram.

7 is a diagram showing the state of the DNP at room temperature depending on the solvent for a compound having a different structure that is not coordinated imine (X = DNP).

8 shows the VT ¹ H NMR spectrum of 7 in THF-d ₈ .

9 is a ¹ H NMR spectrum showing the reaction of Compound 10 or 8 with propylene oxide. The signal marked "*" is a new signal derived from the negative ions of Meisenheimer's salt.

Claims (20)

delete delete delete delete delete delete delete delete delete delete The complex of formula (8). [Formula 8]

[In Formula 8, R ⁹² and R ⁹⁴ are methyl, R ⁹¹ and R ⁹³ is-[CH {(CH ₂ ) ₃ N ⁺ Bu ₃ } ₂ ] or-[CMe {(CH ₂ ) ₃ N ⁺ Bu ₃ } ₂ ], Q is trans-1,2-cyclohexylene or ethylene, b + c is 5, one of 5 X is BF ₄ , and two are 2,4-dytrophenolate And two are anions of the formula (9). [Formula 9]

Where R ¹⁰¹ is methyl or hydrogen.] An alkylene oxide having 2 to 20 carbon atoms which is unsubstituted or substituted with halogen or alkoxy, using a complex of the formula (8) as a catalyst; Cycloalkene oxide having 4 to 20 carbon atoms unsubstituted or substituted with halogen or alkoxy; And copolymerizing an epoxide compound selected from the group consisting of styrene oxides having 8 to 20 carbon atoms and unsubstituted or substituted with halogen, alkoxy, or alkyl, and carbon dioxide. [Formula 8]

[In Formula 8, R ⁹² and R ⁹⁴ are methyl, R ⁹¹ and R ⁹³ is-[CH {(CH ₂ ) ₃ N ⁺ Bu ₃ } ₂ ] or-[CMe {(CH ₂ ) ₃ N ⁺ Bu ₃ } ₂ ], Q is trans-1,2-cyclohexylene or ethylene, b + c is 5, one of 5 X is BF ₄ , and two are 2,4-dytrophenolate And two are anions of the formula (9). [Formula 9]

Where R ¹⁰¹ is methyl or hydrogen.] The solution obtained by dissolving the copolymer and the catalyst obtained by the method of preparing polycarbonate according to claim 12 is brought into contact with a solid phase selected from inorganic materials, high molecular materials and mixtures thereof, which are not dissolved in the solution. Forming a complex to separate the copolymer solution; In a medium in which the solid phase cannot be dissolved, treating the complex with a metal salt of an acid or non-reactive anion to perform acid-base reaction or salt metathesis reaction; And Salt metathesis reaction using a salt comprising an X anion; Comprising, a method of separating and recovering a complex. (X is the same as X in claim 12.) The method of claim 13, The solution in which the copolymer and the catalyst are dissolved is added to a solution in which a solid phase selected from an inorganic material, a polymer material and a mixture thereof is dissolved, and then filtered, or the solution in which the copolymer and the catalyst is dissolved is filled into the solid phase. And separating and recovering the recovered compound by passing it through a separated column. The method of claim 13, And the solid inorganic material is a surface-modified or unmodified silica or alumina, and the solid polymer is a compound having a deproton-reactive functional group by an alkoxy anion. The method of claim 15, The deprotonated reactive functional group is a sulfonic acid group, a carboxylic acid group, a phenol group, or an alcohol group by said alkoxy anion. The method of claim 13, Separating the copolymer by contacting the copolymer obtained by the method for preparing a polycarbonate and the catalyst in accordance with claim 12 with silica to form a silica-catalyst complex; In a medium in which silica cannot be dissolved, treating the silica-catalyst complex with a metal salt of an acid or non-reactive anion to perform acid-base reaction or salt metathesis reaction; And Salt metathesis reaction using a salt comprising an X anion; Comprising, a method of separating and recovering a complex. The method according to claim 13 or 17, Wherein said acid is hydrochloric acid or 2,4-dinitrophenol, and the metal salt of the non-reactive anion is DBF ₄ or DClO ₄ (D is Li, Na or K). The method according to claim 13 or 17, The salt containing the X anion is a salt comprising a 2,4-dinitrophenolate anion, characterized in that the recovery method of the complex. delete

Images