MXPA97008388A - Method for the preparation of catalyst - Google Patents

Abstract

The present invention relates to: A method for the preparation of a metal carbene, in which a first-reacting metal salt, in the presence of a base and a secondary or tertiary alcohol, is a tertiary phosphine or phosphite, or a diphosphine or diphosphate diphtheriates, and is then reacted, in the presence of an acid, with an alkyne and, if desired, with an alkane

Description

METHOD FOR THE PREPARATION OF CATALYSTS The present invention relates to a method for the preparation of ruthenium and osmium carbene catalysts. The polymerization of thermal metathesis of cycloolefins subjected to stress, which has recently acquired great importance, requires catalysts that are primarily transition metal compounds. Whereas, initially, systems consisting of catalysts and co-catalysts were used (see, for example, US 4 060 468 and WO 93/13171), one-component catalysts are also known [Thoi, HH Ivin, KJ, Rooney, JJ, J. Mol. Catal. 15: 245-270 (1982)]. More recently, the so-called "metal carbenes", composed of ruthenium and osmium having a group = CR * R ** attached to the metal atoms, have been found to be especially interesting compounds for that application [patent WO 93/20111; Kanao a, S., Grubbs, R. H., Macromolecules 38: 4707-4713 (1995); Fraser, C., Hillmyer, M., Gutierrez, R., Grubbs, R. H., Poly. Prepr. 36: 237-238 (1995); Schwab, P., France, M. B., Ziller, J. W. Grubbs, R. H., Angew. Chem., 197: 2179-2181 (1995)]. That type of compound is also suitable for catalyzing the ring closure in dienes (WO 95/04289).

Schwab et al. [Schwab P., Grubbs, R.H., Ziller, J.W., J. Am. Chem. Soc. 118: 100-110 (1996); Schwab, P., France, M. B. Ziller, J. W. Grubbs, R. H. Angew, Chem. Int. Ed. Engl. 34: 2039-2041 (1995)] describes the synthesis of ruthenium carbennes with the use of diazoalkanes. In WO 96/04289, the synthesis of vinyl ruthenium carbenes using cyclopropenes is described. Both diazoalkanes and cyclopropenes are thermally unstable and are not commercially available. Therefore, it is necessary to prepare them first in a complicated method briefly before the synthesis. Also, diazoalkanes are generally toxic and difficult to handle, due to their explosive nature. Grünwald et al. [Grünwald, C., Gevert, O., Wolf, J., Gonzalez-Herrero, P., Werner, H., Organometallics 15: 1960-1962 (1966)] describe the preparation of ruthenium carbene catalysts using alkynes , a 100% excess of phosphines and H2 pressure • Surprisingly, it has now been found that the ruthenium and osmium carbenes can be synthesized very well using the salts of Ru or Os, which can be easily obtained, and an alkyne , and, if desired, an alkene. In the process of the invention, the use of H2 is superfluous. This process can be carried out under normal pressure and in the presence of water. In addition, thermally unstable cyclopropene or diazoalkane compounds are not used. Only reagents are used, commercially available and of low price. In comparison with the method described by Grünwald et al. [Grünwald, C., Geven O., Wolf, J. Gonzalez-Herrero, P., Werner, H., Organome tal lies 15"1969-1962 (1966)], the reaction proceeds very quickly, less phosphite is used / Ru and the yield is also higher The compounds prepared by the method of the invention are extremely suitable as catalysts in the polymerization of cyclic olefins and in the ring closure of dienes The invention relates primarily to a process for the preparation of a composed of the formula: in which: I am ruthenium or osmium; x01 and x02 are each, independently of each other, halogens; T1 and T2 are each, independently of each other, a phosphine or tertiary phosphite, or T1 and T2 together form a diphosphine or diteriatrial diphosphite; and T3 is hydrogen, alkyl (C? -C2o) t cycloalkyl (Cß-Cg), heterocycloalkyl (C3-C7), having one or two heteroatoms, selected from the group of oxygen, sulfur and nitrogen, aryl (Cg-Ci4) or (C 4 -C 15) heteroaryl, having one to three heteroatoms, selected from the group of oxygen, sulfur and nitrogen, in which alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl are unsubstituted or substituted by alkyl (C 1 -C 4) , haloalkyl (C? -C4), (C1-C4) alkoxy, (C6-C10) aryl / (C6-C10) aryloxy, -N02 or by halogen; in which a metal salt of the formula: wherein: Me, X01 and X02 have the above definitions, L1, L2, L3 and L4 are each, independently of each other, a neutral ligand and n is 0 - or 1; it is reacted first, in the presence of a base and a secondary or tertiary alcohol, with a phosphine or tertiary phosphite or a diphosphine or di-tertiary diphosphite, and then reacted in the presence of an acid or an alkyne of the formula: HC = C - T3 (III) where T3 has the above definitions. The present invention also relates to a process for the preparation of a compound of the formula: in which: I am ruthenium or osmium; X01 and X02 are each, independently of each other, halogens; ijil and > ? > 2 are each, independently of each other, a phosphine or tertiary phosphite, or T1 and T2 together form a diphosphine or diphtheriate diphosphite; and T3 is hydrogen, alkyl (^^ 20) cycloalkyl (C3-Cg), heterocycloalkyl (C3-C7), having one or two heteroatoms, selected from the group of oxygen, sulfur and nitrogen, aryl (C6-C14) or heteroaryl (C4-C15), having one to three heteroatoms, selected from the group of oxygen, sulfur and nitrogen, in which the alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl are unsubstituted or substituted by (C1-C4) alkyl, haloalkyl ( C1-C4), (C1-C4) alkoxy, aryl (C6-Cl?), Aryloxy (C6-C10) ~ N02 ° By halogen; wherein a compound of the formula: where Me, T1 T2, T3, Xo1, X02 have the above definitions, is reacted with an alkene of the formula: H2C = CH - T3 (Illa) where T3 has the above definitions. Me in formulas I and is preferably ruthenium. According to the invention, halogen is F, Cl, Br or I. X01 and X02 in formulas I and is preferably F, Cl or Br, especially Cl or Br, and more especially are each Cl.

The phosphines and tertiary phosphites and diphosphines and di-tertiary diphosphites preferably contain from 3 to 40, especially from 3 to 30 and more especially from 3 to 24 carbon atoms. The phosphines or tertiary phosphites and diphosphines or diphtheriates diphtheriates preferably correspond to the formulas: PR1R2R3 (IV) RlR2p_Z-pRlR2 (IVa) P OR1) (OR2) OR3 (IVb) R1- OP (OR2) -Z- (OR2) POR1 (IVc) wherein: R1, R2 and R3 are each, independently of each other, alkyl (CÍ-C20) cycloalkyl (C4-C12), heterocycloalkyl (C2-C1;), aryl (C6-C16) or heteroaryl (C2-) C15), in which the alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and aralkyl are unsubstituted or substituted by alkyl (C ± -C6), alkoxy (C ^ Cg), haloalkoxy (Ci-Cg), aryl (C6-C16) , -N02, SO3, ammonium and halogen, the radicals R1 and R2 together form a tetra- or para-methylene, which is unsubstituted or substituted by (C1-C6) alkyl, haloalkyl (Ci-Cg), -N02, or by alkoxy (Ci-Cg), or tetra- or penta-methylene, which is unsubstituted or substituted by alkyl (C ^ -Cg), haloalkyl Ci-C), -N02, or by alkoxy ^ -Cg) and condensed with one or two 1, 2-phenylene (s), and R 3 has the above definitions; and Z is a linear or branched (C2-Ci2) alkylene, unsubstituted or substituted by (C1-C4) alkoxy; 1,2- or 1,3-cycloalkylene unsubstituted or substituted by alkyl (C? -C4) or alkoxy (C? -C4), having from 4 to 8 carbon atoms; 1,2- or 1,3-heterocycloalkylene unsubstituted or substituted by (C 1 -C 4) alkyl or (C 1 -C 4) alkoxy, having 5 or 6 ring and non-heteroatom members of the group of one O atom and one atom of N, 1,2-phenylene unsubstituted or substituted by (C 1 -C 4) alkyl or (C 1 -C 4) alkoxy; l-methylene-phen-2-yl; 1,2-dimethylenebenzene or 2,2'-biphenylene unsubstituted or substituted by alkyl (C? -C4) or (C1-C4) alkoxy. The neutral ligands in the definition of L1, L2, L3 and L4, are preferably the alkylene (C2-C12), cyclo-alkene (C3-C12), arene (Cg-C ^), heteroarene (C4-C12), a ether, a fasphine, a phosphite, a nitrile, an isonitrile, a dialkyl sulfoxide, H 2 O or an amine. Examples of alkyl are methyl, ethyl and propyl isomers, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. An example of the alkyl substituted with aryl is benzyl. Examples of alkoxy are methoxy, ethoxy and the isomers of propoxy and butoxy. Examples of alkylene are methylene, ethylene and the isomers of propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene and dodecylene. Examples of the alkene are ethene, propene, butene, butadiene, pentene and the isomers of pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene and hexatriene and the isomers of heptatriene, octatriene, nonatriene and decatriene. Some examples of cycloalkyls are cyclo-butyl, cycloheptyl, cyclooctyl and especially cyclopentyl and cyclohexyl. Examples of the substituted cycloalkyls are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl- and tristrifluoromethyl-cyclopentyl and -cyclohexyl. Examples of cycloalkylenes are 1,2- and 1,3-cyclopentylene and 1,2- and 1,3-cyclohexylene. Examples of cycloalkenes are cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclododecene, cyclohexadiene, cycloheptadiene and the cyclooctadiene and cyclooctatetraene isomers and the bicyclo [2.2. l] -hepta-2, 5-diene. Some examples of heterocycloalkyls are tetrahydrofuranyl, pyrrolidinyl, piperazinyl and tetrahydro-thiophenyl. Examples of heterocycloalkylene are the 1,2- and 1,3-pyrrolidines 1,2- and 1,3-piperidine and also 1,2- and 1,3-tetrahydrofuran. Examples of aryls are phenyl and naphthyl. Examples of aryloxy are phenyloxy and naphthyloxy. Examples of substituted aryls are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistri-fluoromethyl and tristrifluoromethyl-phenyl. An example of aralkyl is benzyl. Examples of substituted aralkyls are methyl-, dimethyl-, trimethyl-, methoxy, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl and tristri-fluoromethyl-1-benzyl. Some examples of heteroaryls are furanyl, thiophenyl, pyrrolyl, pyridinyl and pyrimidinyl. Arenos and heteroarerenes are, for example, benzene, eumeno, biphenyl, naphthalene, anthracene, acenaphthene, fluorene, phenanthrene, pyrene chrysene, fluorantrene, furan, thiophene, pyrrole, pyridine,? -piran,? -thiopyran, pyridine, pyrazine , indole, coumarone, thionaphtene, carbazole, dibenzo-furan, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, isoxazole, isothiazole, quinoline, isoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazines, thianthrene or purine. Nitriles and isonitriles, within the scope of the present invention, are compounds of the formula: R9-CN or R9-NC, wherein R9 is (C1-C1) alkyl / (C3-C8) cycloalkyl, (C3-C7) heterocycloalkyl ), which have one or two heteroatoms, selected from the group of oxygen, sulfur and nitrogen, aryl (Cg-Ci4) or heteroaryl (C4-C15), having one to three heteroatoms, selected from the group of oxygen, sulfur and nitrogen , wherein the alkyl, cycloalkyl, heterocyclealkyl, aryl and heteroaryl are unsubstituted or substituted by (C 1 -C 4) alkyl, (C 1 -C 4) haloalkyl, (C 4 -C 4) alkoxy, aryl (Cg-C 0), aryloxy (Cg-C ^ o) »~ N02 ° By halogen. Examples of dialkyl sulfoxide are dimethyl sulfoxide, diethyl sulfoxide, tetramethylene sulfoxide and pentamethylene sulfoxide. Examples of ethers are dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl or di ethyl ether, ethylene glycol monoethyl or diethyl ether, diethylene glycol diethyl ether and triethylene glycol dimethyl ether. Within the scope of the present invention, the amines correspond to the formula R10R1: LR12N and ammonium, corresponding to the formula R10R11R12N +, wherein R10, R11 and R12 are each, independently of each other, hydrogen, alkyl (C-C13), (C5-Cg) cycloalkyl unsubstituted or substituted by (C-C4) alkyl or (C1-C4) alkoxy-aryl (Cg-C18) unsubstituted or substituted by (C-C4) alkyl or (C-C4) alkoxy, or aralkyl (C6-C18): or R10 and R11 together form tetramethylene, pentamethylene, 3-oxa-l, 5-pentylene or [CH2] 2NH [CH2] 2- or - [CH2] 2N (alkyl (^^ 4)) - [CH2] -, and R12 »independently, has the definition from Rio. The alkyls preferably contain from 1 to 12 and especially from 1 to 6 carbon atoms. The aryls preferably contain from 6 to 12 carbon atoms and the aralkyls preferably contain from 7 to 9 carbon atoms. Examples of amines are methyl-, dimethyl-, trimethyl-, ethyl, diethyl, triethyl-, methyl-ethyl-, dimethyl-ethyl-n-propyl-, di-n-propyl, tri-n-butyl-, cyclohexyl- , phenyl- and benzyl-amine, and also pyrrolidine, N-methylpyrrolidine, piperidine, piperazine, morpholine and N-methylmorpholine. - The radicals R1, R2 and R3 are preferably identical radicals. Likewise, radicals R1, R2 and R3 which are sterically demanded, for example cyclic or branched alkyl groups, especially a, di-branched and more especially branched, are especially preferred. When R1, R2 and R3 are substituted, the substituents are preferably (C-C4) alkyl, halo (C-C4) alkyl, (C1-C4) alkoxy, SO3 or ammonium. The halogen is preferably Cl and especially F. Examples of preferred substituents are methyl, methoxy, ethyl, ethoxy and trifluoromethyl, R1, R2 and R3 may be substituted, for example, by 1 to 3 substituents. R1, R2 and R3, as alkyls, can be linear or branched and preferably contain from 1 to 12, especially from 1 to 8 and more especially from 1 to 6, carbon atoms. Preferred examples are methyl, ethyl, n- and isopropyl, n, iso-sec and tere. -butyl, 1-, 2- or 3-pentyl and 1-, 2-, 3- or 4-hexyl. Branched alkyl groups, sterically demanded, are especially preferred. When R1, R2 and R3 are cycloalkyl, they are preferably (C5-C8) cycloalkyl and especially cycloalkyl (C5-Cg). When R1, R2 and R3 are aryl, they are preferably aryl (Cg-C2) and especially phenyl or naphthyl. When R1, R2 and R3 are aralkyl, they are preferably aralkyl (C7-C13), the alkylene group in aralkyl is preferably methylene. Especially the aralkyl is benzyl. Examples of tetra- and penta-methylene, unsubstituted or substituted and, as the case may be, condensed, linked to the P atom are: Other suitable phosphines are cycloaliphatic and have 6 to 8 carbon atoms in the ring and form a bridge by a group = PR4, for example: wherein R4 is (C ~ Cg) alkyl, cyclohexyl, benzyl or phenyl which is unsubstituted or substituted by one or more (C1-4) alkyl substituents. Z is as a linear or branched alkylene, is preferably 1,2-alkylene or 1,3-alkylene, preferably having from 2 to 6 carbon atoms, for example ethylene, 1,2-propylene or 1,2-butylene . Preference is given to the tertiary phosphines of the formula IV, in which R1, R2 and R3 are each, independently of each other, alkyl (C -C20) 1 cycloalkyl (C4-C2) or aryl (Cg-C g) ), in which the alkyl, cycloalkyl and aryl are unsubstituted or substituted with a substituent, selected from the group consisting of alkyl (C ~ Cg), alkoxy (C ~ Cg), haloalkyl (C-Cg), aryl (Cg-C) g), -N02, S02, ammonium and halogen. Especially preferred examples of tertiary phosphines of the formula IV are (C Hs) 2 (iso-C3H7) P, (C6H5) (iso (C3H7) 2P, (CgHsJzíCgHuJP, (CgHs ^ P, (C6H5CH2) 3P, (C5H9) 3P , (2,3-di-tert.-C4H9-CgH3) 3P, (2,6-di-tert.-C4H9-C6H3) 3P, (3-CH3-6-tert.-C4H9-C6H3) 3P, ( C6H11) 3P, (2-CH3-6-tert.-C4H9-CgH3) 3P, (4-tert.-C4H9-C6H4) 3P, (3-tert-C4H9-C6H4) 3P, (2-tert.-C4H9 -C6H4) 3P, (4-Iso-C4H9-C6H4) 3P, (CH3) 3P, (C2H5) 3P, (n-C3H7) 3P, (iso-C3H7) 3P, (n-C4H9) 3P, (3- iso-C4H9-C6H4) 3P, (2-iso-C4H9-C6H4) 3P, (4-n-C4H9-C6H4) 3P, (3-n-C4H9-C6H4) 3P, (sec-C4H9) 3P, (2 -CH3-C6H4) 3P, (3-CH3-C6H4) 3P, (4-CH3-C6H4) 3P, (2,4-di-CH3-C6H3) 3P, (2,6-di-CH3-CgH3) 3P , (2-C2H5-CgH4) 3P, (3-C2H5-C6H4) 3P, (4-C2H5-C6H4) 3P, (2-n-C3H7-C6H4) 3P, (3-n-C3H7-C6H4) 3P, (3-n-C3H7-C6H4) 3P, (4-n-C3H7-C6H4) 3P, (2-Iso-C3H7-C6H4) 3P, (3-Iso-C3H7-C6H4) 3P, (4-Iso-C3H7 -C6H4) 3P, (C6H5) (CgHn) 2P, (2-n-C4H9-C6H4) 3P, (C6H5) sec.-C4H9) 2P, (C6H11 ([C (C2H4) 2 (N (CH3) C1) ] P, (C6H ??) 2tCH2CH2N (CH3) 3Cl] P, (CgHn) 2 [CH2CH2S03Na] P and (2,4-di-ter-C4H9-C6H3) 3P. Examples of phosphites are (CH30) 3P, (C2H50) 3P, (n-C3H70) 3P, (iso-C3H70) 3P, (n-C4H90) 3, (2,6-di-tert.-C H9-CgH30) 3P, (2,3-di-tert.-C4H9-CgH3?) 3P, (2, 4, di-tert.-C H9-CgH30) 3P, (iso-C4H90) 3P, (4-CH3-C6H40) 3P, (tere.-C4H90) 3P, (CgH50) 3P, (2,4-di-CH3-CgH30) 3P, (2,6-dl-CH3-CgH30) 3P, (2-C2H5-C6H40) 3P, (3-CH3-6-tert.-C4H9-C6H30) 3P, (3-CH3-6-tert.-C4H9-C6H30) 3p, (3-C2H5-CgH40) 3P, (2-CH3-6-tert- C4H9-C6H30) 3P, (4-C2H5-C6H4?) 3P, (2-n-C3H7-C6H40) 3P, (3-n-C3H7-C6H40) 3P, (4-n-C3H7-C6H40) 3P, ( 3-n-C4H9-CgH40) 3P, (2-n-C4H9CgH4?) 3P, (4-n-C4H9-CgH40) 3P, (2-Ís? -C3H7-C6H40) 3P, (3-Ís? -C4H9 -CgH40) 3P, (4-is? (C4H9-CgH40) 3P, (2-CH3-CgH4?) 3P, (3-CH3-CgH40) 3P, (3-iso-C3H7-C6H40) 3P, (4- iso-C3H7-C6H40) 3P, (2-iso-C4H9-C6H0) 3P, (2-tert.-C4H9-CgH4?) 3P, (3-tert.-C4H9-CgH40) 3P and (4-tert-3 C4H9-C6H40) 3P. T3, as alkyl may preferably contain from 1 to 12, and especially from 1 to 8 carbon atoms, T3 is especially linear (C? -Cg) alkyl.T3, as cycloalkyl, may contain preferable 5 to 8 carbon atoms. Cyclopentyl and cyclohexyl are especially preferred. T 3, as heterocyclylalkyl, may preferably contain 4 or 5 carbon atoms and preferably a heteroatom, selected from the group of oxygen, sulfur and nitrogen. T3 as aryl may preferably contain from 6 to 10 carbon atoms. Preferred examples are naphthyl and especially phenyl and substituted phenyl. T 3, as heteroaryl, may preferably contain 4 or 5 carbon atoms and one or two heteroatoms, selected from the group of oxygen, sulfur and nitrogen. Preferred substituents of T3 are methyl, ethyl, methoxy, ethoxy, trichloromethyl, trifluoromethyl, phenyl, phenyloxy, F, Cl, isopropyl, tertiary butyl and OH. In a preferred embodiment, T3 is hydrogen (C-C9) alkyl, cyclopentyl, cyclohexyl, phenyl or naphthyl, which are unsubstituted or substituted by alkyl (C! -C4), alkoxy (C! -C4), haloalkyl (^ - 04), phenyl, F or Cl. For example, T3 is preferably benzyl. A preferred sub-group of the compounds of the formulas I and the, are formed by those of the formulas: wherein: Me is Ru or Os, R5 is a (C3-C8) a-branched alkyl, or cycloalkyl (C5 ~ C8), which is unsubstituted or substituted by alkyl (C ~ C4), haloalkyl (C-) C4), alkoxy (C! -C4), halogen or by -N02, or aryl (C6-C? 0), which is unsubstituted or substituted by alkyl (C! -C), halo- (C1-C4) alkyl , (C-C4) alkoxy, halogen or -N02; and T3 is hydrogen, alkyl (Ci-C) or cycloalkyl (C5-Cg), which is unsubstituted or substituted by alkyl (C? ~ C), haloalkyl (C! -C), (C1-C4) alkoxy, halogen or by -N02, or aryl (Cg-C? o), which is unsubstituted or substituted by alkyl (C ~ C), haloalkyl (C ~ C4), alkoxy (C! -C4), halogen or by -NO2 • Some specific and preferred examples of the formulas I and [Me is Os and preferably Ru [are: Cl2 [P (C6H11) 2-CH2CH2-P (C6H11) 2] Me = CH-C6H5, Cl2 [P (C6H11)] 3] 2Me = CH-C6H4-CH (CH3) 2, Cl2 [P (iso-C3H7) 3] 2 e = CH- [CgH4 (tert-C4H9)], Cl2 [P (C6H11) 3] 2Me = CH2 Cl2 [P (C5H9) 3] 2Me = CH2, Cl2 [P (C6H11) 3] 2Me = CH- [C6H4terc.-C4H9]], C12 [P (C5H9) 3] 2 Me = CH-CH3, Cl2 [P (C6H11) 3] 2Me = CHCH3, Cl2 [P (C6H5) 3] 2Me = CH-C6H5, F2 [P (C5H9) 3] 2Me = CH-C6H5, Br2 [P (CgHn) 3] 2Me = CH-C6H2 - (CH3) 3, Br2 [P (C5H9) 3] 2Me = CH-CgH5, Cl2 [P (C5H9) 3] 2Me = CH-C6H5, Br2 [P (C5H9) 3] 2Me = CH (C6H4-OCH2H5) , Cl2 [P (C5H9) 3] 2Me = CH-CgH5, F2 [P (C6H11) 3] 2Me = CH-C6H5, Cl2 [P (ISSO-C3H7) 3] 2Me = CH- [CgH4 (CH3)], Cl 2 [P (C5H9) 3] 2Me = CH-C6Hn, Cl2 [P (C5H9) 3] 2Me = CH-C6H11, Cl2 [P (C6H2- (CH3) 3) 3] 2Me = CH-C6H5, Br2 [P (C6H11) 3] 2Me = CH-CgH5, Cl2 [P (C6H11) 3] 2Me = CH-C6H5, Br2 [P (C5H4- (CH3) 2) 3] 2Me = CH-C6H5, Br2 [P (C5H9) 3] 2Me = CH-iso-C3H7, Cl2 [P (iso-C3H7) 3] 2Me = CH-C6H5, Br2 [P (C6H11) 3] 2Me = CH (C6H4-N? 2), Cl2 [P (CgH11 ) 3] 2Me = CH-tert.-C4H9, Cl2 [(C5H9) 3] 2Me = CH.-n-C4H9, Cl2 [P (C6H4-CH3) 3] 2Me = CH-C6H5, Cl2 [P (C6H11) 3] 2Me = CH-n-C4H9, Cl2 [P (C6H11) 3] 2Me = CH-C10H9 Cl2 [P (C6H11) 3] 2Me = CH (CH6H4-Cl), Cl2 [P (C5H9) 3] 2Me = CH (C6H4-Br), Cl2 [P (C6H11) 3] 2Me = CH-C6H4-OCH3, Cl2 [P (C5H9) 3] 2Me = CH-CgH3- (CHH3) 2, F2 [P (C5H9) 3] 2Me = CH [CgH3- (CH3) 2], Br2 [P (C5H9) 3] 2Me = CH-CH2C6H5, Cl2 [P (C6H11) 3] 2Me = CH (C6H4-CH3), Cl2 [P (sec-C4H9 ) 3 [2Me = CH-C6H5, BrCl [P (C6H? 1) 3] 2Me = CH-C6H5, BrCl [P- (ISSO-C3H7) 3] 2Me0CH-C6H5, BrCltP CgHu ^^ Me ^ H-CHzCgHs, Cl 2 [P (C 6 H 11) 2 (C (CH 2 CH 2) 2 N (CH 3) 3 Cl)] 2Me = CH-CH 6 H 5, Cl2 [P (C6H11) 2 (CH2CH2S03Na)] 2Me = CHC6H5, Cl2 [P (C6Hn) 2 (CH2N (CH3) 3CH) 2Me = CH-C6H5 and BrCl [P (iso-C3H7) 3] 2Me = CH-CH2C6H5 .

L1, L2, L3 and L4 are preferably selected from the group consisting of H20, alkene (C2-C), cycloalkene (C3-C12) > dimethyl sulfoxide, tertiary phosphine and tertiary amine.

Special preference is given to H2O and cycloalkenes, such as norbornadiene and cyclooctadiene. Within the scope of the present invention, any base (proton acceptor) and any acid (proton donor) are suitable. Preferred bases are those that have a greater basicity than water. Examples are tertiary amines, metal hydroxides, metal alcoholates and metal phenolates. Preferred bases are triethylamine, 1,3-diazobicyclo [5.4.0] undec-7-ene, KOH, NaOH, tertiary KO-butyl and NaO-methyl, especially triethylamine and l, 8-diazabicyclo [5.4 , 0] undec-7-ene. Preferred acids are hydrohalic acids.

Examples are selected from the group consisting of HF, HCl, HBr and Hl, special preference is given to HCl and HBr. The secondary and tertiary alcohols are advantageously compounds of the formula HC (R6) (R7) OH or R6C (R7) (R8) OH, where R6 R7 and R8 are each, independently of each other, alkyl (C? -C2o) or cycloalkyl (C4-Ci2) > which is unsubstituted or substituted by alkyl (C -C), haloalkyl (C? -C6), -N02 or by alkoxy (C-Cg), or aryl (C6-Cig), which is unsubstituted or substituted by alkyl ( Ci-Cg), haloalkyloylCi-Cg), -N02 or by alkoxy (C ^ Cg), or arachyl (C7-C g), which is unsubstituted or substituted by alkyl (C-C6), haloalkylofC ^ Cg), - N02 or by alcoxifC! -Cß); or the radicals R6 and R7 together form tetra- or pentamethylene, which is unsubstituted or substituted by alkyl (C-Cg), haloalkyl (C ± -C), -N02 or by alkoxy (C ^ Cg), or tetra- or penta-methylene, which is unsubstituted or substituted by alkyl (C ~ Cg), haloalkyl (C ~ Cg), -N02 or by alkoxy (C? Cg) and condensed with one or two l, 2-phenylene (s), and R8 has the above definitions. R6, R7 and R8 are preferably each independently of one another (C -C2o) alkyl (C4-C2) cycloalkyl, which is unsubstituted or substituted by alkyl (C ~ Cg), haloalkyl (C-Cg), - N02 or by alkoxy (C ~ Cg), R6, R7 and R8 are especially each, independently of each other, alkyl (C -CIQ) ° (C4-C2) cycloalkyl. Special preference is given to methyl, ethyl, propyl, isopropyl, butyl, isobutyl and secondary butyl. The method of the invention can be advantageously carried out by suspending the metal, base and phosphine or phosphite salt in the secondary or tertiary alcohol. By heating at a temperature in the range of 0 to 150 ° C, preferably 60 to 100 ° C, especially 80 to 90 ° C, the temperature is selected depending especially on the boiling point of the alcohol used, the suspension becomes a solution.

The acid and alkyne are added to the solution, the order in which this is done is not of consequence. It has been found advantageous to add the acid first and only then add the alkyne. A favorable reaction temperature for this step is the range of -1500C to +1502C, preferably -1002C to +602C and especially -802C to room temperature. The process of the invention is carried out especially by: (a) suspending the metal, base and phosphine or phosphite salt in the secondary or tertiary alcohol, (b) heating the suspension to a temperature in the boiling point range of the used alcohol, (c) adding the acid and alkyne to the resulting solution and (d) reacting the reaction mixture at a temperature in the range -1502C to + 1502C. The reaction of the compounds of the formula I is advantageously carried out at a temperature in the range from 0 to 100 ° C., preferably from room temperature to 50 ° C. All the reaction steps are generally carried out under normal pressure, it has been found especially advantageous for the preparation of the compounds of the formula I, to carry out the reaction steps in an inert atmosphere, preferably in a nitrogen atmosphere or of argon.

The mass ratio of the phosphine or phosphite, base, acid or alkyne to the metal salt is generally in the range of 2: 1 to 100: 1, the ratio of 2: 1 is preferred. The mass ratio of the alkene to the compound of the formula I is generally in the range of 1: 1 to 100: 1, preferably 1: 1 to 10: 1, the 5: 1 ratio is especially preferred. The resulting compounds of formulas I and II are prepared by known methods, as described for example in WO 96/04289, Schwab et al. [Schwab. P., Grubbs, RH Ziller, JW, J. Am. Chem. Soc. 118: 100-110 (1995)] and Grünwald et al [Grünwald C., Gevert, O., Wolt, J., González-Herrero, P., Werner, H., Organometallics 15: 1960-1962 (1996)]. Cyclic olefins which can be polymerized using the catalysts prepared according to the invention are known and described, for example, in WO 96/24629 (FM / 6-20336 / A). They are preferably monocyclic or polycyclic ring systems, condensed and / or bridged and / or bonded, having for example two to four rings, which are unsubstituted or substituted and can contain heteroatoms, for example an O, S atom, N or Si, in one or more rings and / or may contain condensed aromatic or heteroaromatic rings, for example o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene. The cycloolefins are preferably norbornene or derivatives of norbornene, norbornadiene, dicyclopentadiene, cyclopentane, cycloheptene, cyclooctene, cycloctadiene or cyclododecene. Dienes that can be closed in the ring with the use of the catalysts according to the invention are described, for example, in Miller et al. [Miller, SJ Blac well, HE Grubb. "RH, J. Am. Chem. Soc. 118: 9606-9614 (1996) [or in Grubbs et al [Grubbs, RH, Miller, SJ, Fu, G. C, Acc. Chem. Res. 28446-452 (1995)].

The following Examples illustrate the invention more fully.

Example 1: Preparation of Cl2 [P- (iso-C3H7) 3] 2Ru = CH-CH2-C5H5 (a) A suspension of RuCl2 (cis, cis-1,5-cyclooctadiene) (220 mg, 0.78 mmol), 0.22 ml (1.56 mmol) of triethylamine and 0.3 ml of tri-isopropylphosphine in 25 ml of isopropanol was stirred at 80ßC for 15 hours. The resulting red clear solution was cooled to -78dC. After the addition of 0.17 ml of phenylacetylene (1.56 mmol), the temperature of the -502C solution was raised over a period of 10 minutes. The resulting solution, of a dark brown color, was cooled to -78se after the addition of 3 ml of a solution of 1M HCl in diethyl ether (3 mmol), the heat was allowed to rise to 0 ° C over a period of. 15 minutes. The resulting reddish-brown suspension was concentrated in vacuo to a reddish-brown semi-solid residue. The residue was stirred with 8 ml of methanol, it was centrifuged and decanted. The resulting fine residue was stirred with 4 ml of methanol, centrifuged and decanted. By vacuum drying, 95 mg of the objective compound was obtained in the form of a violet powder (purity 50%). (b) A brown suspension of RuCl2 (cis, cis-1, 5-cyclooctadiene) (110 mg: 0.39 mmol) 0.11 ml (0.78 mmol) of triethylamine and 0.15 ml of tri-isopropylphosphine in 13 ml of isopropanol was added. stirred at 80 ° C for 15 hours. The resulting light red solution was cooled to -78dC. After the addition of 0.8 ml of a 1M HCl solution in diethyl ether, stirring was carried out for 5 minutes. After the addition of 0.07 ml of 1-phenylacetylene (0.4 mmol) to the resulting yellow suspension, the temperature was allowed to rise to room temperature over a period of 30 minutes. The resulting brown solution was concentrated under high vacuum and gave a reddish-brown residue. The magnetic-nuclear resonance spectrum (NMR) showed that the expected product was almost pure, with only traces of by-products.

Example 2; Preparation of Cl2 [(iso-C3H7) 3] 2Ru = CH-C5Hn 440 mg of Cl2Ru (cyclooctadiene), 600 μl of tri-isopropylphosphine, 440 μl of triethylamine and 50 ml of isopropanol were placed under nitrogen. The suspension, chestnut colored, was heated to 802C. After 15 hours at 80 ° C, the suspension became a light red solution. 25 ml (0.785 mmol) of that solution were removed and cooled to -78SC. 1.6 ml of the 1M HCl solution (2 equivalents) in diethyl ether were added and stirring was carried out at -78 ° C for 3 minutes. Then 180 μl of 1-hexin was added and the solution was brought to -10 ° C, producing a chestnut-violet suspension, which was concentrated in vacuo at half its volume. After cooling once more to -25CC, subjecting to centrifugation and drying the residue, the title compound was obtained in the form of a dark violet powder (310 mg / 69%).

Example 3: Preparation Cl2 [P (iso-C3H7) 3] 2Ru = CH-C7H15 (a) A suspension of RuCl2 (cis, cis-1,5-cyclooctadiene) (110 mg, 0.39 mmol), 0.11 ml (0.78 mmol ) of triethylamine and 0.15 ml of tri-isopropylphosphine in 13 ml of isopropanol, was stirred at 80 ° C. for 15 hours. The resulting red clear solution was cooled to -78se. After the addition of 0.8 ml of a 1M HCl solution in diethyl ether, stirring was carried out for 5 minutes. After the addition of 0.06 ml of 1-octino (0.8 mmol) to the resulting yellow suspension, the temperature was allowed to rise to the ambient in a period of 15 minutes. The resulting reddish-brown suspension was concentrated in vacuo to a reddish-brown residue. The residue was stirred with 2 x 4 ml of methanol, centrifuged and decanted. The product, a violet powder, was dried under vacuum (yield: 25 mg, 10%) (b) A brown suspension of RuCl2 (cis, cis-1, 5-cyclooctadiene) (440 mg: 1.58 mmol) 0.44 ml (3.15 mmoles) of triethylamine and 0.6 ml of tri-isopropylphosphine in 50 ml of isopropanol was stirred at 85 ° C for 6 hours. The resulting light red solution was cooled to -782C. After the addition of 3.2 ml of a 1M HCl solution in diethyl ether, stirring was carried out for 5 minutes. After the addition of 0.23 ml of 1-octino (1.6-mmoles) to the resulting yellow suspension, the temperature was allowed to rise to -20 ° C. The resulting brown suspension was stirred from -202C to -302C for 30 minutes. Concentration at -52 C under high vacuum gave a reddish-brown residue. The residue was extracted with 25 ml of hexane and, after concentration, gave a semi-solid brown-violet color. The residue was stirred with 20 ml of methanol, which had a temperature of -70 ° C, was centrifuged and decanted. The fine powder, of a dark violet color, was dried under vacuum. The yield is 270 mg (28%) of the pure product.

Example 4; Preparation of Cl [P (iso-C3H7) 3] 2Ru = CH-CH3 A brown suspension of RuCl2 (cis, cis-1,5-cyclooctadiene) (110 mg, 0.39 mmol) 0.11 ml of triethylamine and 0.15 ml of tri-isopropylphosphine in 12.5 ml of isopropanol, was stirred at 85 ° C for 3.5 hours. The resulting light red solution was cooled to -782C. After the addition of 0.8 ml of a 1M HCl solution in diethyl ether, stirring was carried out for 5 minutes. The resulting yellow suspension was heated to 10 ° C over a period of 30 minutes. By the introduction of acetylene (2 bubbles / second), a reddish-brown suspension was obtained, which was concentrated under high vacuum. The resulting reddish-brown residue was stirred with 4 ml of methanol, centrifuged and decanted. The fine violet powder was dried under vacuum. The yield is 105 mg (51%) of the pure product.

Example 5; Preparation of Cl2 [(iso-C3H7 > 3] 2R = CH-CH2-C6H5 440 mg of Cl2Ru (cyclooctadiene), 600 μl of tri-isopropylphosphine, 440 μl of triethylamine and 50 ml of iso-propanol were placed under nitrogen. The chestnut suspension was heated to 85SC. After 3.5 hours at 852C, the suspension became a red solution, 25 ml (0.785 mmol) of that solution were removed and cooled to -782C under nitrogen. 1.58 ml of the 1M HCl solution in diethyl ether were added and stirring was carried out for 5 minutes, yielding a yellow suspension. Acetylene gas (2 bubbles / second) was then introduced for 30 minutes. A violet-colored precipitate was produced. After the addition of 1.5 ml (15 equivalents) of the allyl benzene, the suspension was warmed to room temperature. After cooling to room temperature for 1 hour, the reaction mixture was concentrated and the residue was washed three times with 8 ml of methanol each time. After drying the residue in vacuo, the title compound was obtained in the form of a violet powder (300 mg / 64%).

Example 6; Preparation of Cl2 [P (iso-C3H7) 3] 2Ru = CH-C6H5 (a) A brown suspension of RuCl2 (cis, cis-1, 5-cyclooctadiene) (440 mg, 1.57 mmol) 0.44 ml of tri- ethylamine and 0.6 ml of tri-isopropylphosphine in 50 ml of isopropanol was stirred at 85 ° C for 3.5 hours. The resulting light red solution was cooled to -78se. After the addition of 3.2 ml of a 1M HCl solution in diethyl ether, stirring was carried out for 5 minutes. 0.48 ml of 1-hexene was added to the resulting yellow suspension. The stirred mixture was heated to -10se and stirred for 45 minutes. 3.7 ml of styrene (31 mmol) was added to the resulting brown solution. Stirring for 30 minutes at room temperature and then for 10 minutes at 402C produced a brown solution. After concentration under vacuum, the residue was stirred with 2 x 6 ml of methanol, centrifuged and decanted. The fine violet powder was dried under high vacuum. The yield is 390 mg. (43%) of the pure product. (b) A brown suspension of uCl 2 (cis, cis-1, 5-cyclooctadiene) (220 mg, 0.78 mmol), 0.22 ml of triethylamine and 0.3 ml of tri-isopropylphosphine in 25 ml of isopropanol was stirred at 95 ° C. during 3 hours. The resulting solution was light red and cooled to -782C. After the addition of 1.6 ml of a 1M HCl solution in diethyl ether, stirring was carried out for 5 minutes. 0.35 ml of phenylacetylene was added to the resulting yellow suspension. The stirred mixture was heated to -10 ° C and stirred for 1 hour. 2 ml of styrene (17 mmol) was added to the resulting suspension of violet color. Stirring for 1.5 hours at room temperature produced a stirred mixture of dark violet color, which was concentrated under high vacuum. The residue was stirred with 5 ml of methanol, centrifuged, decanted and stirred with 2 ml of methanol, centrifuged and decanted. The fine violet powder was dried under high vacuum. The yield of 370 mg (81%) of the pure product.

Example 7: Preparation of Cl2 [P (iso-C3H7) 3] 2 u = tertiary CH-C6H4-C4H9 A brown suspension of RuCl2 (cis, cis-1,5-cyclooctadiene) (220 mg, 0.78 mmol), 0.22 ml of triethylamine and 0.3 ml of tri-isopropylphosphine in 25 ml of isopropanol was stirred at 952C for 3.5 hours. The resulting solution of light red color cooled to -78se. After the addition of 1.6 ml of a 1M HCl solution in diethyl ether, stirring was carried out for 5 minutes. 0.24 ml of 1-hexane was added to the resulting yellow suspension. The stirred mixture was heated to -152C and stirred for a period of 15 minutes and at 02C for a period of 30 minutes. 1.45 ml of 4-tert. -butylstyrene (7.85 mmoles) to the resulting suspension of reddish brown. Stirring for 20 minutes at room temperature produced a dark violet solution, which was concentrated under high vacuum. The resulting liquid mixture, of a dark violet color, consisted of the pure product and the 4-tert. -butylstyrene and could be used, for example, directly in solvent-free polymerizations of DCPC.

Example 8; Preparation of Cl2 [(iso-C3H7) 3] 2Ru = CH-C6H4-CH3 A chestnut suspension of RuCl2 (cis, cis-1,5-cyclooctadiene) (110 mg, 0.39 mmol) 0.11 ml of triethylamine and 0.15 ml of tri-isopropylphosphine in 12.5 ml of isopropanol, was stirred at 85 ° C for 3.5 hours. The resulting light red solution was cooled to -782C. After the addition of 0.8 ml of a 1M HCl solution in diethyl ether, stirring was carried out for 10 minutes. 0.1 ml of 1-hexyne (0.63 mmol) was added to the resulting yellow suspension. The stirred mixture was heated, with stirring, to -ÍO ^ C for a period of 30 minutes and at 02C for a period of 15 minutes. 0.42 ml of 4-methylstyrene was added to the resulting suspension of violet color. Agitation for 30 minutes at room temperature produced a violet solution, which was concentrated under high vacuum. The resulting violet-colored residue was extracted three times with 15 ml of hexane each time and, after concentration, gave a semi-solid residue of violet color. The residue was stirred with 10 ml of methane, which has a temperature of 0 ° C, was centrifuged and decanted. The fine violet powder was dried under high vacuum. The yield is 105 mg (56%) of the pure product.

Example 9; Preparation of Cl2 [P (C6H? 1) 3] Ru = CH-C6H5 A brown suspension of RuCl2 (cis, cis-1,5-cyclooctadiene) (440 mg, 1.57 mmol), 0.47 ml of l, 8-diazabicyclo [5.4.0] undec-7-ene (3.14 mmol) and 8 ml of a 20% solution of tri-cyclohexylphosphine in toluene in 25 ml of isopropanol was stirred for 85 hours for 2 hours. The resulting light red solution was cooled to O ^ C. After the addition of 6.3 ml of a 1M HCl solution in diethyl ether to the resulting orange suspension, stirring was carried out for 10 minutes, 0.48 ml of 1-hexane was added to the resulting orange suspension. The stirred mixture was warmed to room temperature and stirred for 45 minutes. After the addition of 3.6 ml of styrene (31 mmol), the stirring was carried out for 2.5 hours. The resulting solution of violet color was concentrated. The residue was taken once more in 25 ml of isopropane, 4 ml of styrene were added and stirring was carried out for 1 hour. After concentration under high vacuum, the residue was stirred with 3 x 8 ml of acetone, centrifuged and decanted. The fine, violet powder was dried under high vacuum. The yield is 450 mg (35%) of the pure product.

Example 10; Preparation of Cl2 [P (iso-C3H7) 3 2Ru = CH-C6H5 A brown suspension of RuCl2 (cis, cis-1,5-cyclooctadiene) 5.25 g; 18.7 mmoles), 5.25 ml (37.4 mmoles) of triethylamine and 7.5 ml of tri-isopropylphosphine in 250 ml of isopropanol, was stirred at 90 ° C for 3.5 hours. The solution, light red, was cooled to -70dC. After the addition of 37.5 ml of a 1M HCl solution in diethyl ether, the stirring was carried out for 15 minutes. 3.75 ml of 1-pentyne was added to the yellow suspension. The stirred mixture was heated to-lose and stirred for 1.5 hours. 21.5 ml of styrene (187 mmol) was added to the resulting suspension of violet color. Stirring for 1 hour at room temperature produced a stirred mixture of dark violet color, which was concentrated in vacuo. The residue was stirred with 30 ml of methanol, centrifuged, decanted, stirred with 5 ml of methanol, centrifuged, decanted and again stirred with 5 ml of methanol, centrifuged and decanted. The fine violet powder was dried under vacuum. The yield is 7.7 g (71%) of the pure product.

Example 11; Preparation of Cl2 [P (C6H11) 3] 2Ru = CH-C6H5 A brown suspension of RuCl2 (cis, cis-1,5-cyclooctadiene) (1.32 g, 4.7 mmoles), 1.42 ml of 1.8- diazabicyclo [5.4.0] undec-7-ene (9.4 mmoles) and 15 ml of a 20% solution of tri-cyclohexylphosphine in toluene in 50 ml of isopropanol was stirred at 80 ° C for 1 hour. The light red solution was cooled to 0 ° C. The addition of 50 ml of tetrahydrofuran produced a clear solution. After the addition of 1.9 ml of 1-pentyne, the stirring was carried out for 10 minutes. 9.4 ml of the 1M HCl solution in diethyl ether was added to the clear solution. The mixture was warmed to room temperature and stirred for 1.5 hours. 5.4 ml of styrene (47 mmol) was added to the violet suspension. Stirring for 1 hour at room temperature produced a stirred mixture of dark violet color, which was concentrated in vacuo. The residue was extracted with 30 ml of hexane / CH2Cl2 (9: 1), decanted and concentrated in vacuo. The residue was stirred with 15 ml of acetone, centrifuged and decanted. The fine violet powder was dried under high vacuum. The yield is 1.9 g (49%) of the pure product.

Claims (10)

1. A method for the preparation of a compound of the formula: in which: I am ruthenium or osmium; X01 and X02 are each, independently of each other, halogens; r1 and r2 are each, independently of each other, a phosphine or tertiary phosphite, or T1 and T2 together form a diphosphine or diteriatrial diphosphite; and T3 is hydrogen, alkyl (C! -C20), cycloalkyl (C3-C8), heterocycloalkyl (C3-C7), having one or two heteroatoms, selected from the group of oxygen, sulfur and nitrogen; aryl (C6-C4) or heteroaryl (C4-C5), having one to three heteroatoms, selected from the group of oxygen, sulfur and nitrogen; wherein alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl are unsubstituted or substituted by alkyl (C -C4), haloalkyl (C! -C4), alkoxy (C1-C4), aryl (Cg-C or), aryloxy (C6) -C10), -N02 or by halogen; in which a metal salt of the formula: where: Me, Xo1 and X02 have the above definitions, L1, L2, L3 and L4 are each, independently of each other, a neutral ligand and n is 0 or 1; it is reacted first, in the presence of a base and a secondary or tertiary alcohol, with a phosphine or tertiary phosphite or a diphosphine or di-tertiary diphosphite, and is then reacted in the presence of an acid or an alkyne of the formula: HC = C (III) where T3 has the above definitions.

2. A method for the preparation of a compound of the formula: in which: I am ruthenium or osmium; X01 and X02 are each ^, independently of each other, halogens; r1 and rp2 are each, independently of each other, a phosphine or tertiary phosphite, or T1 and T2 together form a diphosphine or diteriatrial diphosphite; and T3 is hydrogen, alkyl (C-C2Q), cycloalkyl (C3-C3), heterocycloalkyl (C3-C7), having one or two heteroatoms, selected from the group of oxygen, sulfur and nitrogen, aryl (Cg-C4) or (C4-C15) heteroaryl, having one to three heteroatoms, selected from the group of oxygen, sulfur and nitrogen, in which the alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl are unsubstituted or substituted by alkyl (C -C4), haloalkyl (C1-C4), alkoxy (C1-C4), aryl (Cg-Cio) 1 aryloxy (Cg-C o), -N02 or by halogen; wherein a compound of the formula: wherein: Me, T1 T2, T3, X01, X02 have the above definitions, are reacted with an alkene of the formula: H2C = CH - T3 (Illa) where T3 has the above definitions.

3. A method according to claim 1 or claim 2, wherein Me is ruthenium.

4. A method according to claim 1 or claim 2, wherein X01 and X02 are Cl.

5. A method, according to claim 1 or claim 2, wherein the tertiary phosphines or phosphites and the diphosphines or Diphtheritic diphosphites correspond to formulas IV, IVa, IVb or IVc: PR1R2R3 (IV) R1R2P-Z-PR1R2 (IVa) P OR1) (OR2) OR3 (IVb) R1-OP (OR2) -Z- (OR2) POR1 (IVc) in which: R1, R2 and R3 are each, independently of each other, alkyl (C ~ C20), cycloalkyl (C4 ~ C2), heterocycloalkyl (C2-ll) 'aryl ° (c6-c16) ° heteroaryl (C2-C5), in which the alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and aralkyl are unsubstituted or substituted by alkyl (C ~ Cg), alkoxy ( C ~ Cg), haloalkoxy (C ~ Cg), aryl (Cg-C16), -N02, SO3, ammonium and halogen, the radicals R1 and R2 form? "- together a tetra- or para-methylene, which is unsubstituted or substituted by alkyl (C ~ Cg), haloalkyl (C? ~ Cg), -NO2, or by alkoxy (C ~ Cg), or tetra- or penta-methylene, which is unsubstituted or substituted by alkyl (C ~ Cg) , haloalkyl (C ~ Cg), -N02, or by alkoxy (C ~ Cg) and condensed with one or two l, 2-phenylene (s), and R3 has the above definitions, and Z is an alkylene (C2) -C 2), linear or branched, unsubstituted or substituted by (C-C4) alkoxy, 1,2- or 1,3-cycloalkylene unsubstituted or substituted by alkyl (C-C4) or alkoxy (C-C4), having from 4 to 8 carbon atoms; 1,2- or 1,3-heterocycloalkylene unsubstituted or substituted by alkyl (C-C4) or (C1-C4) alkoxy, having 5 or 6 ring and non-heteroatom members of the group of one O atom and one atom of N, 1,2-phenylene unsubstituted or substituted by alkyl (C-C4) or alkoxy (C! -C4); l-methylene-phen-2-yl; 1,2-dimethylenebenzene or 2,2 * -biphenylene unsubstituted or substituted by (C-C4) alkyl or (C-C4) alkoxy.

6. A method, according to claim 1 or claim 2, wherein T1 and T2 correspond to a tertiary phosphine of formula IV, wherein R1, R2 and R3 are each, independently of each other, alkyl (C-) C2Q) (C4-C12) cycloalkyl or aryl (Cg-Cig), in which the alkyl, cycloalkyl and aryl are unsubstituted or substituted by a substituent selected from the group consisting of alkyl (Cx-C), alkoxy ( C ~ Cg), haloalkyl (C? -C6), aryl (C6-c? G), -N02, SO3, ammonium and halogen.

7. A method, according to claim 6, wherein T1 and T2 are: (C6H5) 2 (is? -C3H7) P, (C6H5) (is? (C3H7) 2P, (C6H5) 2 (CgHn) P , (C6H5) 3P, (C6H5CH2) 3P, (C5H9) 3P, (2, 3-di-tert.-C4H9-C6H3) 3P, (2,6-di-tert.-C4H9-C6H3) 3P, (3-CH3-6-tert.-C4H9-C6H3) 3P, (c6Hll) 3p / (2-CH3-6-tert.-C4H9-CgH3) 3P, (4-tert.-C4H9-C6H4) 3P, (3-tert-C4H9-C6H4) 3P, (2-tert. C4H9-CgH4) 3P, (4-iso-C4H9-C6H4) 3P, (CH3) 3P, (C2H5) 3P, (n-C3H7) 3P, (iso-C3H7) 3P, (n-C4H9) 3P, (3 -iso-C4H9-CgH4) 3P, (2-iso-C4H9-C6H4) 3P, (4-nC4H9-C6H4) 3P, (3-n-C4H9-C6H4) 3P, (sec-C4H9) 3P, ( 2-CH 3 -C 6 H 4) 3 P, (3-CH 3 -C 6 H 4) 3 P, (4-CH 3 -CgH 4) 3 P, (2, 4-di-CH 3 -C 6 H 3) 3 P, (2,6-di-CH3-C6H3) 3P, (2-C2H5-C6H4) 3P, (3-C2H5-C6H4) 3P, (4- C2H5-C6H4) 3P, (2-n-C3H7-C6H) 3P , (3-n-C3H7-C6H4) 3P, (3-n-C3H7-C6H4) 3P, (4-n-C3H7-CgH4) 3P, (2-iso-C3H7-C6H4) 3P, (3-iso- C3H7-C6H4) 3P, (4-Iso-C3H7-C6H4) 3P, (C6H5) (CgHn) 2P, (2-n-C4H9-C6H4) 3P, (C6H5) sec.-C4H9) 2P, (CgH11) [C (C2H4) 2 (N (CH3) Cl)] P, (CgHn) 2 [CH2CH2N (CH3) 3C1] P, (C6H11) 2 [CH2CH2S03Na] P and (2, 4-di-ter- C4H9-C6H3) 3P.

8. A method, according to claim 1 or claim 2, wherein T3 is hydrogen, (C ~ C9) alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl or naphthyl, which are unsubstituted or substituted by alkyl (C ~ C4), (C-4) alkoxy, haloalkyl (C-C4), phenyl, F or by Cl. A method, according to claim 1 or claim 2, wherein the compounds of the formulas I and they are those of the formulas Ib and you: wherein: Me is Ru or Os, R5 is a (C3-C8) a-branched alkyl, or (C5-C8) cycloalkyl, which is unsubstituted or substituted by alkyl (C-C4), haloalkyl (C1-) C4), alkoxy (C! ~ C4), halogen or by -NO2, or aryl (Cg-C o) which is unsubstituted or substituted by alkyl (C! -C4), haloalkyl (C ~ c4), alkoxy (C ~ C), halogen or by -N02; and T3 is hydrogen, alkyl (C? ~ Cg) or cycloalkyl (C5-Cg), which is unsubstituted or substituted by alkyl (C ~ C4), haloalkyl (C ~ C4), alkoxy (C ~ C4), halogen or by -NO2 or aryl (Cg-C o), which is unsubstituted or substituted by alkyl (C! -C4), haloalkyl (C ~ C4), alkoxy (C ~ C), halogen or by -N0. 10. A method, according to claim 1 or claim 2, wherein the compounds of the formulas I and the are: Cl2 [P (C6Hn) 2-CH2CH2-P (C6Hn) 2] Me = CH-C6H5, Cl2 [P (C6H11) 3] 2Me = CH-C6H4-CH (CH3) 2, Cl2 [P (iso-C3H7) 3] 2Me = CH- [CgH4 (tert-C4H9)], Cl2 [P (C6H11)] 3] 2Me = CH2, Cl2 [P (C5H9) 3] 2Me = CH2, Cl2 [P (CgHi!) 3] 2Me = CH- [C6H4tere. -C4H9)], C12 [P (C5H9) 3] 2 Me = CH-CH3, Cl2 [P (C6H11) 3] 2Me = CHCH3, Cl2 [P (C6H5) 3] 2Me = CH-CgH5, F2 [P ( C5H9) 3] 2Me = CH-C6H5, Br2 [P (C6H11) 3] 2Me = CH-C6H2- (CH3) 3, Br2 [P (C5H9) 3] 2Me = CH-C6H5, 43 aCl2 [P (C5H9) 3] 2Me = CH-C6H5, Br2 [P (C5H9) 3] 2Me = CH (C6H4-OC? 2H5), Cl2 [P (C5H9) 3] 2Me = CH-C6H5, F2 [(C6H11) 3] 2Me = CH-C6H5, Cl2 [P (Iso-C3H7) 3] 2Me = CH- [C6H4 (CH3)], C12 [P (C5H9) 3 2Ke = CE-C6K11, Cl2 [? > (C5H9) 3] 2Ke = C? -C6H11, Cl2 [P (C6H2- (CH3) 3) 3] 2Me = CH-C6H5, Br2 [P (C6H11) 3] 2Me = CH-C6H5, Cl2 [P (C6H11 ) 3] 2Me = CH-C6H5, Br2 [P (C5H4- (CH3) 2) 3] 2Me = CH-C6H5, Br2 [P (C5H9) 3] 2Me = CH-iso-C3H7, Cl2 [P (I- C3H7) 3] 2Me = CH-C6H5, Br2 [P (C6H1?) 3] 2Me = CH (C6H4-N02), Cl2 [P (C6H11) 3] 2Me = CH-tert.-C4H9, Cl2 [(C5H9) 3] 2Me = CH. -n-C4H9, Cl2 [P (C6H4-CH3) 3] 2Me = CH-C6H5, Cl2 [P (C6H11) 3] 2Me = CH-n-C4H9, Cl2 [P (C6H11) 3] 2Me = CH-C10H9 , Cl2 [P (C6HU) 3] 2Me = CH (CH6H4-Cl), Cl2 [P (C5H9) 3] 2Me = CH (C6H4-Br), Cl2 [P (CeHn) 3] 2Me = CH-C6H4-OCH3 , Cl2 [P (C5H9) 3] 2Me = CH-C6H3 - (CHH3) 2, F2 [P (C5H9) 3] 2Me = CH [C6H3- (CH3) 2], Br2 [P (C5H9) 3] 2Me = CH-CH2C6H5, Cl2 [P (C6H11) 3] 2Me = CH (C6H4-CH3) f Cl2 [P (sec-C4H9) 3 [2Me = CH-C6H5, BrCl [P (C6H11) 3] 2Me = CH-C6H5 , BrCl [P- (ISSO-C3H7) 3] 2MeOCH-C6H5, BrCl [P (C6H11) 3] 2Me = CH-CH2C6H5, Cl2 [P (C6H11) 2 (C (CH2CH2) 2N (CH3) 3Cl)] 2Me = CH-CH6H5, Cl2 [P (C6H11) 2 (CH2CH2S03Na)] 2Me = CHC6H5, Cl2 [P (C6HU) 2 (CH2N (CH3) 3CH) 2 - = CH-C6H5 and BrCl [P (iso-C3H7) 3 ] 2Me = CH-CH2C6H5, where Me is Os or Ru.