MXPA98004906A - Catalysts bis and tris (pirazolil) borato metalicos comple - Google Patents

Abstract

The present invention relates to metal complexes of the formula (I) or (Ii) which are suitable for the oligomerization and polymerization of olefinically unsaturated compounds and for the copolymerization thereof with carbon monoxide, wherein M is a metal of the subgroup of the Periodic Table of the Elements, E is an element of the main group 5 of the Periodic Table of the Elements, R1 to R11, R15 are substituents that are selected from the group consisting of hydrogen, organocarbon radicals of C1 to C30 and organosilicon radicals from C3 to C30, and are substituents that are selected from the group consisting of organocarbon radicals of C1 to C30 and organosilicon radicals of C3 to C

Description

CATALYSTS BIS AND TRIS (PIRAZOLIL) BORATO MET LICOS COMPLEJOS The present invention relates to the metal complexes of the formulas (I) and (I ') which are suitable for the oligomerization and polymerization of olefinically unsaturated compounds and for the copolymerization thereof with Rβ R2 carbon monoxide R5 where M is a metal of the subgroup of the Periodic Table of the Elements, E is an element of the main group 5 of the Table Periodic of the Elements, R1 to R11, R15 are substituents that are selected from the group consisting of hydrogen, organocarbon radicals of Ci to C3o and organosilicon radicals of C3 to C3o, and R12 to R14 are substituents selected from the group consisting of organocarbon radicals from Ci to C30 and C3 to C3o organosilicon radicals, and to catalyst systems which are suitable for the oligomerization and polymerization of the olefinically unsaturated compounds and the copolymerization thereof with carbon monoxide, comprising, as the active constituents, A ) a metal complex of the formula (I) R8 R2 R5 or a metal complex of the formula (I '(I') » R5 where M is a metal of the subgroup of the Periodic Table of the Elements, E is an element of the main group 5 of the Table Periodic of the Elements, R1 to R11 R15 are substituents that are selected from the group consisting of hydrogen, organocarbon radicals of Ci to C3o and organosilicon radicals of C3 to C3o, and R12 to R14 are substituents that are selected from the group consisting of radicals organocarbon from Ci to C3o and organosilicon radicals from C3 to C30, and B) a Lewis acid The present invention also relates to a process for the preparation of metal complexes of the formula (I) R8 R2 R5 or r R2 R5 by reacting a halometallic complex of the metal with a tris (pyrazolyl) borate anion of the formula (II). or with a bis (pyrazolyl) borate anion of the formula (II ' where in (I), (I '), (II) or (II'), M is a metal of the subgroup of the Periodic Table of the Elements, M 'is lithium, sodium, potassium, rubidium, cesium, magnesium, calcium or lithium, E is an element of the main group 5 of the Table Periodic of the Elements, R1 to R11 R15 are substituents that are selected from the group consisting of hydrogen, organocarbon radicals of Ci to C30 and organosilicon radicals of C3 to C30, and R12 to R14 are substituents that are selected from the group consisting of radicals organocarbon of Ci to C3o and organosilicon radicals of C to C3u n is 1 or 2, where n is the formal valence of M ', also refers to a process for the preparation of oligomers and polymers of olefinically unsaturated compounds and copolymers of olefinically unsaturated compounds and carbon monoxide polymerizing the monomers from 0 to 300 ° C and from 1 to 500,000 kPa in the presence of a metal complex of the formula (I).

Rß R2 : i ') R2 R5 where M is a metal of the subgroup of the Periodic Table of the Elements, E is an element of the main group 5 of the Periodic Table of the Elements, R1 to R11 R15 are substituents that are selected from the group consisting of hydrogen, organocarbon radicals of Ci to C3o and organosilicon radicals of C3 to C30, and R12 to R14 are substituents selected from the group consisting of organocarbon radicals of Ci to C30 and organosilicon radicals of C3 to C3o, and a process for the preparation of oligomers and polymers of olefinically unsaturated compounds and of copolymers of olefinically unsaturated compounds and carbon monoxide by the polymerization of monomers of O at 300 ° C and from 1 to 500,000 kPa in the presence of a catalyst system comprising, as active constituents, A) a metal complex of the formula (1) R8 R2 (I) R5 or a metal complex of the formula (I ') R2 R5 wherein M is a metal of the subgroup of the Periodic Table of the Elements, E is an element of the main group 5 of the Periodic Table of the Elements, R1 to R11 R15 are substituents that are selected from the group consisting of hydrogen, organocarbon radicals from Ci to C3o and organosilicon radicals of C3 to C30 / and R1"and Rl4 are substituents selected from the group consisting of organocarbon radicals of Ci to C30 and organosilicon radicals of C3 to C30, and B) a Lewis acid The present invention also relates to the use of a metal complex of the formulas (I) and (I ') according to claim 1 as a catalyst for the preparation of oligomers and polymers of olefinically unsaturated compounds and for the preparation of copolymers of olefinically unsaturated compounds and carbon monoxide, and the use of a catalyst system as claimed in claim 4 for the preparation of oligomers and polymers of olefinically unsaturated compounds and for the preparation of copolymers of olefinically unsaturated compounds and carbon monoxide.

Metal complexes of metals of subgroup 8 of the Periodic Table of Elements such as nickel have hitherto been used in olefinic oligomerizations (W. Keim, Angew.Chem (1990), pages 251 ff) or in olefin copolymerizations. carbon monoxide, palladium (E. Drent et al., in "Ziegler-Natta Catalysts", G. Fink, R. Mühlhaupt, HH Brintzinger (editors), Springer Verlag, Berlin (1995), pages 482 ff) or nickel ( US 3,984,388; US 5,214,126). However, none of the metal complexes or catalysts used was without disadvantages; either of these were complicated in their preparation, costly, had unsatisfactory activity or required temperatures or polymerization processes; excessively high. An object of the present invention is to provide metal complexes of formulas (I), and (I ') and catalyst systems containing (I) or (I') that do not have the aforementioned disadvantages, or only to a lesser degree, that have superior productivity and that are easily accessible. Another object of the present invention was to provide a process for the preparation of metal complexes of the formulas (I) and (I ') and a process for the preparation of oligomers and polymers of olefinically unsaturated compounds and a process for the preparation of copolymers of olefinically unsaturated compounds and carbon monoxide in the presence of metal complexes of the formulas (I) and (I '), or in the presence of the catalyst systems and the use of metal complexes of the formulas (I) or (I'), or of catalyst systems for the preparation of oligomers and polymers of this type. We have found that this objective is achieved by the metal complexes of the formulas (I) and (I '), defined at the beginning and by the catalyst systems defined at the beginning, by a process for the preparation of the metal complexes of the formulas (I ) and (I '), by a process for the preparation of oligomers and polymers of olefinically unsaturated compounds and of copolymers of olefinically unsaturated compounds and carbon monoxide in the presence of the metal complexes of the formulas (I) or (I'), or in the presence of the catalyst systems defined at the beginning, and by using the metal complexes of the formulas (I) and (I '), and by using the catalyst systems defined at the beginning for the process for preparing the oligomers and polymers of olefinically unsaturated compounds or for the preparation of copolymers of these compounds and carbon monoxide. Suitable M metals in the metal complexes of formulas (I) and (I ') are those of subgroup 8 (VIIIB) of the Periodic Table of the Elements, ie, iron, cobalt, ruthenium, rhodium, osmium, iridium , platinum, palladium and very specifically nickel. In complexes, metals can formally have a double positive charge. Suitable elements E are those of the main group V (group 5a), of the Periodic Table of the Elements, that is, nitrogen, phosphorus, arsenic, antimony, or bismuth. Nitrogen and phosphorus, in particular phosphorus, are particularly suitable. The radicals R "to R11 and R15 can be hydrogen or organocarbon or organocarbon radicals.The organocarbon radicals R1 to R11 and R15 are aliphatic, cycloaliphatic and very specific aromatic radicals., in each case with 1 to 30 carbon atoms. The radicals which may be mentioned by way of example are linear and preferably branched C 1 to C 1 alkyl groups, such as methyl, ethyl, 1-propyl, isopropyl, 1-butyl, sec-butyl, tert-butyl and 1-hexyl. Suitable cycloaliphatic radicals which may be mentioned are C3 to C6 cycloalkyl radicals such as cyclohexyl. Particularly suitable organocarbon radicals R1 to Ru and R15 are aromatic radicals, which can also be substituted, for example, C1 to C6 alkyl radicals, by other Cd-C10 aryl radicals, or by halogens, such as fluorine, chlorine bromine, or iodine or alternatively by perfluoro alkyl radicals, such as the trifluoromethyl, pentafluoroethyl, heptafluoro propyl or heptafluoro isopropyl radicals. If the aryl radicals do not carry any other carbon substituent, they preferably contain from 6 to 20 carbon atoms. The alkyl aryl radicals Rx to R? which are substituted by alkyl groups or derivatives thereof will preferably have from 1 to 10 carbon atoms in the alkyl radical and from 6 to 10 carbon atoms in the aryl radical. The aromatic ring can, of course, also be replaced several times. Examples which may be mentioned of the highly suitable radicals R 1 to R 1 are phenyl 1-naphthyl, 2-naphthyl, ortho-tolyl, meta-tolyl, p-tolyl, 2,4,6-tri-ethylphenyl (mesityl), 2- (trifluoromethyl) -phenyl, 2,6-di (trifluoroethyl) phenyl, 2,6-dimethylphenyl and 2,4-dimethylphenyl. Suitable organosilicon radicals R1 to R11 and RlD having from 3 to 30 carbon atoms are preferably tri-organosilyl radicals containing C 1 to C 0 alkyl radicals C 6 to C 1 aryl radicals, such as trimethylsilyl, triethylsilyl, triphenylsilyl or ter -butyldimethylsilyl.

The radicals R12, R13 and R14 can have the same meaning as the organo carbon and organo silicon radicals R1 to Ru. However, the radicals R12, R13 and R14 are generally not hydrogen. The metal complexes of the formulas (I) and (I ') which have proved to be very highly suitable are those in which Ru R12, R1J, R14, R3 and R6 and in some cases also R9 are aromatic radicals of the aforementioned types for these substituents, preferably phenyl or ortho-tolyl, and in which R 10, R 15 and the substituents on the pyrazolyl rings R 1, R 2, R 4 R 5, R 7 and R 8 are hydrogen. Examples of the very particularly preferred metal complexes of formulas (I) and (I ') are [(hydrotris (3-phenylpyrazolyl) borate) (ortho-tolyl) triphenylphosphine)] nickel (II) [(hydrotris (3-p)] -tolipirazolyl) borate) (ortho-tolyl) triphenylphosphine)] nickel (II), and [(hydrotris (3-phenylpyrazolyl) borate) (ortho-tolyl) tri p-tolyl phosphine)] nickel (II).

A particularly preferred metal complex of the formula (I ') is [. { dihydrobis (3-phenylpyrazolyl) borate} (ortho-tolyl) (triphenylphosphine)] nickel (II). It has been found advantageous to react the novel metal complexes of the formulas (I) and (! ') With a compound B) which is capable of binding the ligand ER1' Ri3 R14 more strongly than the metal M. The compounds which are Suitable for this purpose, in general are the Lewis acids, which, according to Römpps Chemie Lexikon, Georg Thieme Verlag, Stuttgart, New York, (1990), page 2499, represent electron pair acceptors. The chemical nature of Lewis B) acids is not important in general, magnesium, boron, aluminum, gallium, silicon, germanium, tin, phosphorus, arsenic, antimony, titanium, zirconium and cadmium halides are the suitable compounds. metals of preference in their highest formal oxidation state. Other suitable Lewis acids are the carbocation salts, such as triphenyl methyl tetrafluoro borate. The examples that can be mentioned of the acids of Lewis specifically suitable are boron trifluoride, the complex boron trifluoride diethyl ether, boron dibromide, tris (pentafluoro phenyl) boron, aluminum trichloride and magnesium dichloride. Good results, in particular in the oligomerization and polymerization of the olefinically unsaturated compounds, have been achieved by using the complex boron trifluoride diethyl ether as component B).

The molar ratio between component A and Lewis acid B) in general is from 0.01: 1 to 1: 1, preferably from 0.02: 1 to 1: 1. As component A) the catalyst systems can, of course, also contain mixtures of different metal complexes of the formula (I) or (I '). The novel metal complexes of the formulas (I) and (I ') are advantageously prepared by substitution of a halogen atom, ie fluorine, bromine or iodine, in an oxygen-metal complex of the metals M by a ligand. bis- or tris (pyrazolyl) borate. For this purpose, a metal compound of the main group of the formula (II) or (II ') wherein M 'is lithium, sodium, potassium, rubidium, cesium, magnesium, calcium or, preferably thallium, n, as the formal valence of M', is 1 or 2, and R1 to R15 are as specified above with the The formulas (I) or (I ') are usually reacted with a metal-halogen complex of the metal M, in particular nickel or palladium, preferably. in an organic solvent such as dichloromethane, toluene, tetrahydrofuran or diethyl ether. Solvent mixtures, for example, acetone / dichloromethane, are preferably also used for the preparation of the metal complexes of the formula (I '). The halogen-metal complex that is preferably used is one of the formula M (ER 12 R) 13, 1 * 2 (R '1X,) X (III), wherein M, E, and R11 to R14 are as defined above for formula (I) or (I '), and X is fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.

The reaction is generally carried out from (-) 80 ° C to 200 ° C, preferably from 0 ° C to 100 ° C. The novel metal complexes of the formula (I) or (I ') and the catalyst systems can be used for the preparation of oligomers and polymers of olefinically unsaturated compounds and for the preparation of copolymers, in general alternating copolymers, of olefinically unsaturated monomers and carbon monoxide (polyketones). Suitable olefinically unsaturated compounds are in principle all monomers of this class of compounds. Preference is given to ethylene and alkoxides of C3 to C14, such as 1-butene, 1-hexene and mainly propene, and also butadiene and also cyclo-olefins, such as cyclopentene, cyclohexene, norbordene and norbordaniene and their derivatives. The olefinically unsaturated aromatic monomers that may be mentioned are mainly styrene and alpha-methyl styrene. Also of importance are acrylic acid and methacrylic acid and derivatives thereof, in particular nitriles, amides and C6 alkyl esters, for example, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate and methacrylate. methyl.

Other suitable monomers are vinyl chloride, vinyl acetate, vinyl propionate, maleic anhydride and N-vinylpyrrolidone. Of course, it is also possible to use mixtures of different monomers, the proportion of the mixture not being generally important. The molar ratio between the olefinically unsaturated compounds, preferably ethylene, propene, 1-butene or 1-hexene and carbon monoxide can be chosen in a substantially free manner and is preferably 0.01: 1 to 100: 1, preferably in the region of 1: 1. The polymerizations for the preparation of the oligomers and polymers of olefinically unsaturated compounds and of the carbon monoxide copolymers can be carried out batchwise or continuously.

Pressures from 1 to 500,000 kPa, preferably from 200 to 350,000 kPa, in particular from 500 to 30,000 kPa, and temperatures from 0 to 300 ° C, preferably from 20 to 250 ° C, in particular from 40 to 150 ° C C have proven to be adequate. The polymerization reactions using the metal complexes of the formula (I) or (I ') or the catalyst systems defined at the beginning can be carried out in gas phase, in suspension, liquid or super critical monomers or in solvents which they are inert under the conditions of the polymerization. Suitable inert solvents are alcohols, such as methanol, ethanol, propanol and -propanol, 1-butanol and tert-butanol, sulfoxides and sulfones, for example, dimethyl sulfoxide, esters such as ethyl acetate and butyrolactone, ethers such as tetrahydrofuran, dimethylethylene glycol and diisopropyl. ether, and preferably aromatic solvents such as benzene, toluene, ethylbenzene and chlorobenzene or mixtures thereof. The molecular weight of the novel polymers can be modified in a manner known to the person skilled in the art by varying the temperature of the polymerization, by means of protic compounds such as alcohols, for example, methanol, ethane or tert-butanol, preferably methanol, and adding hydrogen. In general, a high concentration of the regulating substances and / or a high polymerization temperature produces a relatively low molecular weight and vice versa. Oligomers, preferably those of C2-C2 alk-1-ene or ethylene and propene, generally have a degree of polymerization, defined by the NMR13C analysis of the final group, from 2 to 1000, preferably 2 to 100, in particular from 2 to 50.

The higher polymers, preferably those of C 1 -C 0 alkylates such as ethene, propene, 1-butene, 1-hexene and 1-octene, generally have a molecular weight Mw, determined by permeation chromatography in gel at 135 ° C in 1, 2, 4-trichlorobenzene compared to the polyethylene standard, in the range of 30,000 to 3,000,000 and an Mw / Mn ratio in the range of 1.5 to 5.0. The molecular weights Mw (weighted average) of the carbon monoxide copolymers (measured by gel permeation chromatography (GPC) at 25 ° C using Shodex® HFIP 803 or 805 as column material and hexafluoroisopropanol as solvent against the standard of polymethyl methacrylate) are generally in the range from 1000 to 1, 000,000, preferably from 1,000 to 100,000. The molecular weight distribution Mw / Mr? (weighted average / numerical average), as measured by gel permeation chromatography (GPC) as described above, of the carbon monoxide copolymers is, in general, from 1 to 50, preferably from 1 to 20. Because of their numerous functional groups, the novel carbon monoxide copolymers can be modified using conventional chemical reactions, as described in, for example, EP-A 372,602, or a combination of the two methods.

Examples Example 1: Synthesis of [. { hydrotis (3-phenylpyrazolyl) orate} (ortho-tolyl) (triphenylphosphine)] nickel (II) 2.00 g (2.7 mmol) of [NiBr (o-tol) (PPh3) 2] were dissolved in 25 ml of dichloromethane at room temperature under a nitrogen atmosphere, and 1.71 g (2.7 mmol) of [T1. { HB (3-Ph-pyrazolyl) 3.}. ] were added. The solution was stirred for 60 minutes, and the formed TIBr was filtered. 10 ml of hexane were added and the solution was concentrated to about 5 ml under reduced pressure, the resulting yellow solid was washed with little hexane until the solvent remained colorless. The complex was then dissolved in little toluene, the solution was filtered, 10 ml of hexane was added and the mixture was evaporated to dryness. The analytically pure product was recrystallizable from diethyl ether. Yield: 1.89 g (82%). iH-NMR (CDC13): 1.60 ppm (s, 3 Hr CH3-tolyl), 5.51 ppm (dt, 1 H, tolyl), 5.78 ppm (d, 1 H, pz, 3 JHH-2.3 Hz), 6.04 ppm < d, 1 H, pz, 3JRH ~ 2.1 Hz), 6.20 ppm (m, 2 H, tolyl), 6.52 ppm (d, 2 H, J ~ 8.1 Hz), 6.69 ppm (m, 6 H), 6.87 ppm (d, 1 H, pz, 3 JHH ~ 2.1 Hz), 7.06 ppm (m, 6 H), 7.41 ppm (m, 19 H), 8.01 ppm (d, 2 H, j ~ 7.2 Hz), 8.28 ppm (d, 1 H, pz, 3 JHH ~ 2.2 Hz) (dß-toluene): 2.13 ppm (s, 3 H, CH3-tolyl), 5.83 ppm (d , 1 H, pz, 3jHH - 2.1 Hz), 6.51 ppm (m, 2 H, tolyl), 6.94 - 7.61 ppm (m, H), 7. 81 ppm, (m, H), 8.36 ppm < d, 2 H, J - 7.1 Hz), 8.42 ppm (d, 1 H, pz, 3 JHH ~ 2.2 Hz) 13C. { 1 HOUR} -NMR: 23.2 ppm, 103.1 ppm, 106.3 ppm, 107.1 ppm, 119.8 ppm, 122.7 ppm, 126.7 ppm, 127.7 ppm (d, JPC ~ 13.9 Hz), 128.0 ppm, 128.2 ppm (d, Jpc ~ 9.7 Hz), 128.5 ppm, 129.1 ppm, 129.3 ppm, 130. 0 ppm, 130.1 ppm, 130.4 ppm, 130.7 ppm, 134.5 ppm (d, JPC ~ 9.8 Hz), 135.0 ppm, 135.1 ppm, 135.4 ppm, 135.7 ppm, 139.6 ppm, 140. 1 ppm (d ", JPC - 5.2 Hz), 146.3 ppm 31P {! H.}. - MR: 18.4 ppm (s) IR (KBr): 2382 v (BH) w, 1468 w, 1438 wr 1433 , 1371 w, 1280 w, 1207, 1180 w, 1103 w, 1088 w, 1070 w, 1051 w, 1038 w, 751 s, 736 w, 696 s, 530 m. Elemental analysis: (C4H? 0O), calculated: C 72.51 H 5.87 N 9.06; found: C 72.12 H 5.81 N 9.07.

Examples 2 to 4: catalytic oligoarizations 102 mg (1.12 mmol) of: [. { hydrotis (3-phenylpyrazolyl) borate} (ortho-tolyl) (triphenylphosphine) Jniquel (II) were dissolved in 50 ml of toluene, 0.6 ml (4.1 mmol, B: Ni = 35: 1) complex of boron trifluoride diethyl ether were added if desired, in the mixture then it was oligomerized for 16 hours under a monomer pressure of 4000 kPa.

The products of the reaction were analyzed by gas chromatography (coupling GC / MS) (column: ultra 2 crosslinked, coated with 5% phenyl silicone, 95% methylsilicone, 25 m * 0.2 mm, 50 to 200 ° C; 5 ° C / min; carrier gas nitrogen). The parameters and results of the experiment are shown in Table 1.

Table 1: Oligomerization of alkanes 3 í Example 5: Preparation of polyketone 102 mg (0.12 mmol) of [. { hydrotis (3-fetyylpyrazolyl) orate} (ortho-tolyl) (triphenylphosphine)] nickel (II) in 50 ml of toluene were reacted for 16 hours at 60 ° C in the presence of 0.3 mole of ethylene (4000 kPa) and 14.3 mmol of carbon monoxide (350 kPa). The solvent was then removed yielding 1.15 g of polyketone (IR: V-0 -1691, i3c-N R: 36.4 ppm, singlet, 212.7 ppm, singlet, H, -5770, M ^ / Mn-1.3.

Example 6 Synthesis of [. { dihydrobis-3-renylpyrazolii) borate] (ortho-ol 11) (triphenylphosphine) nickel (il)] Bimoimolar amounts of KÍH2B (3-Ph-pi? Azolyl) 2] (223.9 mg, 0.66 mino)) and [NiBr (o-tol) (PPh3) 2J (500.0 mg, 0.66 mmol) were subjected to stirring in a mixture of acetone / dichloromethane (15 ml / 15 ml) with nitrogen for 16 hours. The resulting precipitate was filtered and the filtrate, after the addition of about 5 ml of n-hexane, was concentrated under reduced pressure to 5 ml, in the course of which a yellow precipitate was produced which was washed with little hexane until .the solvent remained pale yellow until colorless. The precipitate was dried under reduced pressure and subsequently washed several times with little acetone to remove the paramagnetic impurities. The product was dried under reduced pressure. Yield: 130 mg (28%). iH-MR (CDC13): 2.20 ppm (s, 3H, CH3, o-tol), 5.70 ppm (d, 1H, pz, 3jHH _ 2.3 Hz), 6.00 ppm (d, 2H, o-tol, 3JHH - 6-4 Hz), 6.25-6.37 ppm (m, 3H, o-tol), 7.01 ppm (d, 1H, pz, 3JHH - 2.2 Hz), 7. 1-8.3 ppm (+ m + d, 27H, PPh3, pz, Ph); 3iP. { iH} -NMR (CDCl 3): 22.56 ppm (s, PPh3); IR (KBr): 2420 cpr1 vBH) Example 7 Preparation of polyketone 56 mg (0.10 mmol) of [. { dihydrobis (3-phenylpyrazolyl) borate} (ortho-tolyl) (triphenylphosphine) ñique (II)) were dissolved in 10 ml of toluene and the solution was stirred in a key car (100 ml) with ethene pressure of 40 bar carbon monoxide pressure of 3.5 bar at 60 ° C for 16 hours. The precipitated polyketone was filtered and washed with tetrahydrofuran. Yield: 1.05 g

Claims (9)

1. A metal complex of the formula (I) or (I ') which are suitable for the oligomerization and polymerization of olefinically unsaturated compounds and for the copolymerization thereof with carbon monoxide R8 R2 R5 wherein M is a metal of the subgroup of the Periodic Table of the Elements, E is an element of the main group 5 of the Periodic Table of the Elements, R1 to Ru, R15 are substituents that are selected from the group consisting of hydrogen, radicals organocarbon from Ci to C30 and organosilicon radicals from C3 to C30, and R12 to R14 are substituents that are selected from the group consisting of organocarbon radicals of Ci to C30 and organosilicon radicals of C3 to C30,

2. The metal complex as claimed in claim 1, wherein M is nickel.

3. The metallic filler as claimed in claim 1 or 2, wherein R3, R6, R9 and Ru to R14 are C3-C2o aryl or C7-C30 alkyl aryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 10 carbon atoms in the aryl radical, and R10 and R15 are hydrogen

4. A suitable catalyst system for the oligomerization and polymerization of the olefinically unsaturated compounds and the copolymerization thereof with carbon monoxide, comprising, as the active constituents, A) a complex or metal of the formula (i; Rß R2 R5 or a metal complex of the formula (I ') R2 (I '), R5 wherein M is a metal of the subgroup of the Periodic Table of the Elements, E is an element of the main group 5 of the Periodic Table of the Elements, R1 to R11 R15 are substituents that are selected from the group consisting of hydrogen, organocarbon radicals from Ci to C30 and organosilicon radicals of C3 to C30, and R "to R are substituents selected from the group consisting of organocarbon radicals of Ci to C3o and organosilicon radicals of C3 to C3o, B) a Lewis acid

5. A process for the preparation of a metal complex of the formula (I): Rβ R2 RS I ') R2 (i ') » R5 by reacting a halometallic complex of the metal with a tris (pyrazolyl) borate anion of the formula (II). or with a bis (pyrazolyl) borate anion of the formula (II ') where in (I), (I '), (II) or (II'), M is a metal of the subgroup of the Periodic Table of the Elements, M 'is lithium, sodium, potassium, rubidium, cesium, magnesium, calcium or lithium, E is an element of the main group 5 of the Periodic Table of the Elements, R1 to R11 R15 are substituents selected from the group consisting of hydrogen, organocarbon radicals of Ci to C30 and organosilicon radicals of C3 to C30, Y R12 to R14 are substituents selected from the group consisting of organocarbon radicals of Ci to C30 and organosilicon radicals of C3 to C30, n is 1 or 2, wherein n is the formal valence of M '.

6. A process for the preparation of oligomers and polymers of olefinically unsaturated compounds and copolymers of olefinically unsaturated compounds and carbon monoxide by polymerizing the monomers from 0 to 300 ° C and from 1 to 500,000 kPa in the presence of a metal complex of the formula (I) R8 R2 R5: i ' R2 (I '), R5 wherein M is a metal of the subgroup of the Periodic Table of the Elements, E is an element of the main group 5 of the Periodic Table of the Elements, R1 to R11 R15 are substituents that are selected from the g-ipo consisting of hydrogen , organocarbon radicals of Ci to C30 and organosilicon radicals of C3 to C3O and R12 to R14 are substituents selected from the group consisting of organocarbon radicals of Ci to C3o and organosilicon radicals of C3 to C30,

7. A process for the preparation of oligomers and polymers of olefinically unsaturated compounds and of copolymers of olefinically unsaturated compounds and carbon monoxide by the polymerization of monomers from 0 to 300 ° C and from 1 to 500,000 kPa in the presence of a catalyst system comprising, as active constituents, A) a metal complex of the formula (I) Rß R2 R5 or a metal complex of the formula (I ') R2 (I '), R5 wherein M is a metal of the subgroup of the Periodic Table of the Elements, E is an element of the main group 5 of the Periodic Table of the Elements, R1 to R11 R15 are substituents that are selected from the group consisting of hydrogen, organocarbon radicals Ci to C3O and organosilicon radicals of C3 to C30, and R12 and R14 are substituents selected from the group consisting of organocarbon radicals of Ci to C30 and organosilicon radicals of C3 to C3o, and B) a Lewis acid

8. The use of a metal complex (I) or (I ') as claimed in claim 1 as a catalyst for the preparation of oligomers and polymers of olefinically unsaturated compounds and for the preparation of copolymers of olefinically unsaturated compounds and carbon monoxide.

9. The use of a catalyst system as claimed in claim 4 for the preparation of oligomers and polymers of olefinically unsaturated compounds and for the preparation of copolymers of olefinically unsaturated compounds and carbon monoxide. SUMMARY OF THE INVENTION The present invention relates to metal complexes of the formula (I) or (I ') which are suitable for the oligomerization and polymerization of olefinically unsaturated compounds and for the copolymerization thereof with carbon monoxide R8 R2 wherein M is a metal of the subgroup of the Periodic Table of the Elements, E is an element of the main group 5 of the Periodic Table of the Elements, R1 to R11, R15 are substituents that are selected from the group consisting of hydrogen, radicals organocarbon of Ci to C30 and organosilicon radicals of C3 to C3o, and R12 to R14 are substituents selected from the group consisting of organocarbon radicals of Ci to C30 and organosilicon radicals of C3 to C3o,