MXPA00004295A - Method for producing fulvene metal complexes - Google Patents

Abstract

The invention relates to a method for producing fulvene metal complexes, to novel metal complexes and to the use of said complexes as catalysts for polymerising unsaturated compounds, especially for polymerising and copolymerising olefins and/or dienes.

Description

PROCEDURE FOR OBTAINING FULVENO METALLIC COMPLEXES Field of the invention.

The present invention relates to a process for obtaining fulvene metal complexes, to new metal complexes of floccene as well as to their use as catalysts for the polymerization of unsaturated compounds, especially for the polymerization and for the copolymerization of olefins and / or of dienes.

Background of the invention Metal complexes with cyclopentadienyl ligands have been intensively investigated since the discovery of ferrocene. The use of cyclopentadienyl metal complexes, in particular the use of metallocene complexes in admixture with activating co-catalysts, preferably alumoxanes, has long been known for the polymerization of olefins and diolefins (for example EP-A 69 951, 129 368 351 REF .: 119683 392,485 821,485 823). The metallocenes have been revealed as specific catalysts, with high activity in the polymerization of olefins. To increase the activity, the selectivity, to control the microstructure, the molecular weights and the molecular weight distribution, a plurality of metallocene catalysts or metallocene catalyst systems for the polymerization of olefinic compounds has been developed in recent years.

In relation to metal complexes with fulvene ligands there is little knowledge.

In the J. Am. Chem. Soc. 1997 publication, 119.5132, polymerization catalysts for zwitterionic olefins, which are formed by the reaction of special compounds of (? 6-2, 3,4,5-tetramethylcyclopentadienyl-1-methylene) (? 5-pentamethyl-cyclo-penta- dienyl) zirconium with tris- (pentafluorophenyl) boron or with bis (pentafluoro-phenyl) borane. The synthesis of the compounds of (? 6-2,3,4, 5-tetramethylcyclopentadienyl-1-methylene) (? 5-pentamethylcyclopentadienyl) zirconium is very expensive, a metallocene having to be prepared with ligands of pentamethylcyclopentadienyl, which decomposes in the last stage of the synthesis by a thermolysis reaction. Such thermolysis reactions are described in the literature.

According to Bercaw et al., JACS (1972), 94, 1219 is formed, by thermolysis of bis (? 5-pentamethylcyclopentadienyl) -thitanedimethyl, the fulvene compound of (? 6-2, 3,4,5-tetramethylcyclo? Entadienil) -1-methylene) (? 5-penta-methylcyclopentadienyl) titanmethyl. The thermolysis of pentamethylcyclopentadienyl complexes of zirconium and hafnium is described in the publication by J. Marks et al., JACS (1988), 110, 7701. By means of the thermolysis of bis ((5-pentamethylcyclopentadienyl) zirconiodiphenyl, the fulvene complex of (6-2, 3,4,5-tetramethylcyclopentadienyl-1-methylene) (5-pentamethyl-cyclopentadienyl) zirconiofenyl is formed.

The preparation of the fulvene complexes according to the thermal process is limited to a few structural variants. The thermal process does not always lead to unitary products. It has been described by 0. Wiikinson et al. in J. Chem. Soc. 1960, 1321-1324 the reaction of 6,6-dialkyl-funne with chromium hexacarbonyl or with molybdenum hexacarbonyl. In place of the metallic fulvene complexes, however, cyclopentadienyl metal complexes are obtained. It is described in the J. Chem. Soc. Dalton Trans. (1985), 2037 by M. L. H. Oreen et al., The synthesis of bis (6,6,6,6-difenylfulvene) titanium by reaction of bis (toluene) titanium with 6,6, diphenylfulvene. However, bis (toluene) titanium must be prepared by metal atomic evaporation techniques, which are complicated and expensive. For this, metallic titanium is evaporated and condensed in a matrix together with gaseous toluene. The yield in bis (toluene) titanium is very low. The bis (toluene) titanium is therefore accessible only in a limited proportion. Thus, there was the task of finding an improved process for obtaining fulvene metal complexes, which avoided the aforementioned drawbacks. It has now been found, surprisingly, that fulvene metal complexes can be prepared by reaction of a fulvene compound with a suitable complex of transition metal in the presence of a reducing agent.

Detailed description of the invention. The object of the present invention is therefore a process for the preparation of fulvene metal complexes of the formula (la) or of the formula (Ib) ??? L..M (Ib), where M means a metal of the groups Illb, IVb, Vb, or of the lanthanides or of the actinides of the periodic system of the elements according to IUPAC, A means an anionic ligand, if appropriate or several times bridged, X means hydrogen, means an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, an alkylaryl group with 7 to 40 carbon atoms, an arylalkenyl group with 8 to 40 carbon atoms, a group silyl substituted by a hydrocarbon radical having 1 to 10 carbon atoms, a halogen atom or an amide of the formula NR72, L denotes a neutral ligand, RX, R2, R3, R4, R5, R6 are the same or different and mean hydrogen , halogen, a cyano group, an alkyl group with 1 to 20 carbon atoms, a fluoroalkyl group with the ß carbon atoms, a fluoroaryl group with 6 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms / an aryl group with 6 to 20 carbon atoms , an aryloxy group with 6 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, an alkylaryl group with 7 to 40 carbon atoms, an arylalkenyl group with 8 up to 40 carbon atoms, an alkynyl group with 2 to 10 carbon atoms, a silyl group substituted by hydrocarbon radicals with 1 to 10 carbon atoms, an amino group optionally substituted by hydrocarbon radicals with 1 to 20 carbon atoms, or R, R2, R3, R4, R5, R6 respectively form, together with the atoms to which they are linked, one or more aliphatic or aromatic ring systems, which may contain one or more heteroatoms (O, N, S) and which have from 5 to 10 carbon atoms, R7 means hydrogen, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, an alkylaryl group with 7 to 10 carbon atoms, up to 40 carbon atoms, a silyl group substituted by hydrocarbon radicals with 1 to 10 carbon atoms, an amino group optionally substituted by hydrocarbon radicals with 1 to 20 carbon atoms, m, p means the numbers 0, 1, 2 , 3 or 4, which are produced by the valence and the linked state of M, as well as k means the numbers 1, 2 or 3, and the sum k + m + p amounts to 1 to 5 depending on the degree of oxidation of M, n means a number from 1 to 10, by reaction of a transition metal compound of the formula (lia) or (Ilb) A ^ -Xs (Ha) mXs nM (Hb) wherein A, X, L, M, m, s and n have the meaning indicated above and s means 2, 3, 4, 5 or 6 and s > p, with a fulvene compound of the formula (III) (III), wherein R1, R2, R3, R4, R5 and R6 have the meaning indicated above, in the presence of a reducing agent. The preparation of fulvene metal complexes of the formula () is explained by means of the following reaction scheme: Agen-be reductor Metallic complex of fulvene (I) The reaction can be carried out in a single reaction step, that is to say in a reaction in a single vessel, the order of the addition of the individual components of the reaction not being predetermined. The reaction can also be carried out in separate reaction steps, for example, the transition metal compounds of the formula (Ha) or (Hb) can first be contacted with a reducing agent and reacted in one step of separate reaction, with fulvene compounds of the formula (III). further, preferably, the transition metal compound (lia) or (Hb) will be added first to the fulvene (III) compound, and then the reducing agent will be added. Suitable reducing agents are, for example, alkali metals, alkaline earth metals, aluminum, zinc, alkali metal alloys, such as, for example, sodium-potassium alloy or sodium amalgam, alkaline earth metal alloys, as well as metal hydrides. Examples of metal hydrides are lithium hydride, sodium hydride, magnesium hydride, aluminum hydride, lithium aluminum hydride and sodium borohydride. Special examples of reducing agents are sodium naphthalenide, potassium graphite, lithium alkyls, magnesium butadiene, magnesium anthracene, trialkylaluminium compounds and Grignard reagents. Preferred reducing agents are the alkali metals or the alkaline earth metals, the alkyl lithiums with 1 to 6 carbon atoms, the tri-alkylaluminum compounds with the carbon atoms and the Grignard reagents. Preferred reducing agents are lithium, magnesium, n-butyllithium, as well as triethylaluminum and triisobutylaluminum. Instead of the mentioned reducing agents, an electrochemical reduction can also be carried out. The process for obtaining the fulvene metal complexes of the formula (I) is carried out in a suitable reaction medium at temperatures from -100 to + 250 ° C, preferably from -78 to + 130 ° C, especially preferred from -10 to + 120 ° C. Suitable reaction media are, for example, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, ethers and cyclic ethers. Examples in this regard are unbranched aliphatic hydrocarbons, such as butane, pentane, hexane, heptane, octane, branched aliphatic hydrocarbons, such as isobutane, isopentane, isohexane, cyclic aliphatic hydrocarbons such as cyclohexane, methylocyclohexane, aromatic hydrocarbons, such as benzene , toluene, xylene, and ethers, such as dialkyl ethers, dimethoxyethane and tetrahydrofuran. Mixtures of various solvents are also suitable. The preparation and handling of the fulvene metal complexes of the formula (I) is carried out with the exclusion of air and water under inert gas conditions (protective gas technique). Examples of inert gases are nitrogen or argon. As a protective gas technique, for example, the Schlenk technique, which is generally used for organometallic substances, is suitable. The metal complexes of fulvene of the formula (I) can be isolated or used directly for other reactions. When isolation is required, the secondary products formed according to the usual methods of purification may be separated, for example by filtration. Alternatively, the desired products can also be extracted with a solvent. If necessary, a purification operation, for example recrystallization, can be carried out. Examples of transition metal complexes of the formula (Ha) or (Hb) are those in which M means a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium, A means a pyrazolate of the formula N2C3R 3- where R8 means hydrogen or an alkyl group with 1 to carbon atoms, or an aryl group with 6 to 10 carbon atoms, a pyrazolylborate of the formula R7B (N2C3R83), an alcoholate or phenolate of the formula OR7, a siloxane of the formula 0SiR73, a thiolate of the formula SR7, an acetylacetonate of the formula (R7CO) 2CR7, a diimine of the formula (R7N = CR7) 2-an amidinate of the formula R7C (NR72) 2-a cyclooctatetraenyl of the formula C8HqR78-q where q means 0, 1, 2, 3, 4, 5, 6, or 7, a cyclopentadienyl of the formula C5HqR75-q where q means 0, 1, 2, 3, 4, 5, an indenyl of the formula C9H7-rR7r where r means 0, 1, 2, 3, 4, 5, 6, 7, a fluorenyl of the formula C? 3H9-sR7s where s means 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 as well as an alkyl moiety with 1 to 30 carbon atoms, an aryl moiety with 6 to 10 carbon atoms, as well as an alkylaryl moiety having 7 to 10 carbon atoms. up to 40 carbon atoms, L, X, R7, m, syn have the meaning indicated above. Very particular preference is given to complexes of the transition metals of the formula (la) or (Hb), in which M means titanium, zirconium or hafbio, A means bis (trimethylsilyl) amide, dimethylamide, diethylamide, diisopropylamide, 2,6 -di-terc. -butyl-4-ethylphenolate, cyclooctatetraenyl, cyclopentadienyl, methylcyclopentadienyl, benzylcyclopentadienyl, n-propylcyclopentadienyl, n-butylcyclopentadienyl, iso-butylcyclopentadienyl, t-butylcyclopentadienyl, cyclopentylcyclopentadienyl, octadecylcyclopentadienyl, 1,2-dimethylcyclopentadienyl, 1,3-dimethyl-cyclopentadienyl, 1,3-di-isopropylcyclopentadienyl, 1,3-di-t-butylcyclopentadienyl, l-ethyl-2-methylcyclopentadienyl, 1-isopropyl-3-methylcyclopentadienyl, 1- (n-butyl) -3-methylcyclopentadienyl, 1- (t-butyl) -3-methylcyclopentadienyl, pentamethylcyclopentadienyl, 1,2,3,4-tetramethyl-cyclopentadienyl, 1,2,4-trimethyl-cyclopentadienyl, 1,2, 4-triisopropyl-cyclopentadienyl, 1, 2, -tri (t-butyl) -cyclopentadienyl, indenyl, tetrahydroindenyl, 2-methylindenyl, 4,7-dimethylindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-4- phenylindenyl, fluorenyl or 9-methyl-fluorenyl. X means fluorine or chlorine L, m, s and n have the meaning indicated above. Suitable fulvene compounds are those of the formula (III) in which R1 to R6 mean an alkyl group with 1 to 30 carbon atoms, an aryl group with 6 to 10 carbon atoms, an alkylaryl group with 7 to 40 carbon atoms, especially hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, pentafluorophenyl, methylphenyl, cyclohexyl or benzyl. The preferred compounds of the formula (III) are fulvene compounds of the formula (IV) (IV), or fulvene compounds of the formula (V) where RX, R2, R3 and R4 have the meaning indicated above. Particularly preferred compounds of the formula (III) are 6-cyclohexylfulvene, 6-isopropylfulvene, 6-tert.-butylfulvene, 6-Phenylfulvene, 6- (dimethylamino) -fulvene, 6,6-bis (dimethylamino) fulvene, 6,6-dimethyl fulvene, 6,6-bis (trifluoromethyl) fulvene, 6,6-diphenyl fulvene, 6,6-bis (pentafluorophenyl) fulvene, 6,6-penta-methylene fulvene, 6,6-tetramethoxy fulvene, 6,6-trimethylene fulvene, 2- (2, -cyclopentadien-1-ylidene) -1, 3-dithiolane, 5-benzylidene 1,2,3-triphenyl-1,3-cyclopentadiene, 1,2,3,4-tetramethylfulvene, 1,2,3, 4-tetraphenyl fulvene, 2,3-dimethylfulvene, 2, 3-diisopropylfulvene, 2,3-diphenylfulvene, 1,4-dimethyl-2,3-diphenylfulvene and 1,4-diethyl-2,3-diphenylfuvene. The synthesis of the fulvene compounds of the formula (III), (IV) and (V) can be carried out, for example, according to J. Org. Chem. Vo. 49, No. 11 (1984), 1849. The formula (I) indicated for fulvene metal complexes should be considered as a formal representation of bonding relationships. The binding ratios in the metal complexes depend, among other things, on the central atom, the oxidation level as well as the substituents of the fulvene ligand.

Detailed Description of the Figures Figure 1 shows the constitution of a fulvene metal complex obtainable according to the invention, in perspective representation as obtained by means of X-ray structural analysis. As an example of the compound (6-tert.-butylfuvinyl) chloride ( pentamethylcyclopentadienyl) -titanium. The process according to the invention offers an access to new metal complexes of fulvene of the formula (I), which, for example, can not be formed by thermolysis. Another object of the present invention are therefore fulvene metal complexes of the formula (I), in which M means a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium, k means 1, A, X,, p, R1, R2, R3, R4, R5 and R6 have the meaning indicated above, with the exception of the compounds of the formula (I), in which R1 and R2 mean hydrogen and, simultaneously, R3 , R4, R5 and R6 mean a methyl group and simultaneously A means a pentamethylcyclopentadienyl group or a 'carborandiyl group of the formula C2B9HH. Another object of the present invention is a catalytic system, consisting of a) a metal complex of fulvene of the formula (I), prepared according to the process of the invention, wherein M means a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium, k means 1, A, X, m, p, R1, R2, R3, R4, R5 and R6 have the meaning indicated above. b) a co-catalyst suitable for the activation of the metal complex a) the molar ratio between component a) and component b) being in the range of 1: 0.1 to 1: 10,000, preferably 1: 1 to 1 : 1,000 Suitable co-catalysts are co-catalysts known in the field of metallocene catalysis, such as polymeric aluminoxanes or oligomers, Lewis acids as well as aluminates and borates. In this context, reference will be made especially to the Macromol publication. Symp. Vol. 97, July 1995, pages 1-246 (for alumoxanes) as well as EP 277 003, EP 277 004, Organometallics 1997, 16, 842-857 (for borates), and EP 573 403 (for aluminates). Especially suitable are co-catalysts methylaluminoxane, methylalumoxane modified with triisobutylaluminum as well as diisobutylalumoxane, trialkylaluminum compounds, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, triisooctylaluminum, in addition dialkylaluminum compounds such as diisobutylaluminum hydride, diisobutylaluminum fluoride and diethylaluminum chloride, of substituted triarylaluminum, such as tris (pen-tafluorophenyl) aluminum, as well as ionic compounds, which contain tetrakis (pentafluorophenyl) aluminium anion, such as triphenylmethyl-tetrakis (penta-fluorophenyl) aluminate, as well as tetrakis- (pentafluorophenyl) N, N-dimethyl anilinium aluminate, substituted triarylboron compounds, such as tris- (pentafluorophenyl) boron as well as ionic compounds, containing as tetrakis- (pentafluorophenyl) borate anion, such as triphenylmethyl-tetrakis (pentafluorophenyl) borate , as well as tetraqu is (pentafluorophenyl) 'borate of N, N-dimethylanilinium. Mixtures of various co-catalysts for the activation of the fulvene metal complexes of the formula (I) are also suitable. Another object of the present invention is the use of this new catalytic system for the polymerization of unsaturated compounds, especially olefins and dienes. As polymerization, it will be understood in this case both the homopolymerization and the copolymerization of the mentioned unsaturated compounds. In the polymerization of alkenes with 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, pentene-1, and hexene-1, octene-1, isobutylene and arylalkenes, such as styrene, will be used in particular. As dienes will be used especially: conjugated dienes, such as 1,3-butadiene, isoprene, 1,3-pentadiene, and non-conjugated dienes, such as 1,4-hexadiene, 1,5-heptadiene, 5,7-dimethyl-1,6-octadiene, 4-vinyl-1-cyclohexene, 5- ethylidene-2-norbornene, 5-vinyl-2-norbornene and dicyclopentadiene. The catalysts according to the invention are suitable for obtaining rubbers based on copolymers of ethylene with one or more of the a-olefins mentioned and the aforementioned diene. Furthermore, the catalyst system according to the invention is suitable for the polymerization of cyclo-olefins such as norbornene, cyclopentene, cyclohexene, cyclooctane and for the copolymerization of cycloolefins with ethylene or with α-olefins. The polymerization can be carried out in the liquid phase, in the presence or absence of an inert solvent, or in the gas phase. Suitable solvents are aromatic hydrocarbons such as benzene and / or toluene, or aliphatic hydrocarbons, such as propane, hexane, heptane, octane, isobutane, cyclohexane or mixtures of various hydrocarbons. It is possible to use the catalytic system according to the invention arranged on a support. Suitable support materials include, for example, inorganic or organic polymeric supports, such as silica gel, zeolites, soot, activated carbons, aluminum oxide, polystyrene and polypropylene. In this case, the catalyst system according to the invention can be arranged in a conventional manner on the carrier materials. The methods for the support of the catalyst systems have been described, for example, in US 4 808 561, 4 912 075, 5 008 228 and 4 914 253. The polymerization is carried out, in general, at pressures of 1 to 1,000, preferably from 1 to 100 bar, preferably from 1 to 1,000 bar, and at temperatures from -100 to + 250 ° C, preferably from 0 to + 150 ° C. The polymerization can be carried out in conventional reactors, continuously or discontinuously.

The invention is explained in more detail by means of the following examples. General indications: Obtaining and handling organometallic compounds was carried out with the exclusion of air and humidity under argon protection (Schlenk technique). All necessary solvents were made absolute before use by boiling for several hours on a suitable drying agent and subsequent distillation under argon. The compounds were characterized by means of spectroscopy of 1 H-NMR, 13 C-NMR and mass. Abbreviations: Cp: Cyclopentadienyl Cp *: Pentamethylcyclopentadienyl 'HV: High vacuum RT: Ambient temperature THF: Tetrahydrofuran MS: Mass spectrum EA: Elemental analysis Tg: Vitreous transition temperature (measured DSC) of: Excess diastereomer.

Synthesis of the compounds of the formula (I).

Example 1. Synthesis of fulvene complex by reaction of 6,6-dimethylfulvene with Cp * TiCl 3 in the presence of magnesium [(C5 (CH3) 5) (C5H4) C (CH3) 2TiCl].

Cp * TiCl3 (0.610 g, 2.11 mmol) and 1.05 equivalents of magnesium (0.054 g, 2.21 mmol) were placed in 25 mL of THF. 1.05 equivalents of 6,6-dimethyl fulvene (0.227 g, 2.14 mmol) were added dropwise at room temperature. It was allowed to stir overnight at RT, so that all the Mg was consumed. The solvent in HV was removed and the green residue was taken up in hexane. The solid product was separated by filtration and the solution was concentrated by evaporation to the middle, whereupon bright green platelets precipitated. For crystallization separation, the charge was cooled to -20 ° C. The olive green crystals were isolated and dried in HV. We obtained 0.429 g (59%) of [(C5 (CH3) 5) (C5H4) C (CH3) 2TiCl]. XH-NMR: (C6D6, 300 MHZ): d = 1.16 (s, 3H, C (CH3) 2), 1.70 (s, 15H, C5 (CH3) 5), 1.75 (s, 3H , C (CH3) 2), 3.43, 4.65, 6.03, 6.70 (m, lH, C5H4) ppm. 13 C-NMR: (C6D6, 75 MHZ): 5 = 12, 82 (C5 (CH3) 5) • 22.76, 24.50 (C (CH3) 2), 108, 10 (C (CH3) 2) 117 , 23, 117.46, 120.04, 124, 09 (C4H4), 122, 55 (C5 (CH3) 5), 132.16 (ipso-C5H4) ppm. MS (70eV) m / e / (%): 324 (4 O) [M +], 288 (40) [M + -HC1], 135 (5) [Cp *], 106 (100) [dimethylfulvene].

Example 2. Synthesis of fulvene complex by the reaction of 6,6-dimethyl fulvene with Cp * TiCl 3 in the presence of butyl-lithium, [(Cp *). 400 mg (1.38 mmol) of Cp * TiCl3, 154 mg (1.45 mmol) of 6,6-dimethylfulvene and 1.11 ml (2.76 mmol) of n-butyl lithium in 25 ml were combined. of THF at a temperature of -78 ° C in a Schlenk vessel. It was allowed to slowly warm to 0 ° C and was stirred until the reaction was complete for another 2 hours at this temperature. The solvent was then removed in HV and the green residue was taken up in n-hexane. The solid product was separated by filtration and the solution was concentrated halfway, whereupon green crystals precipitated. 290 mg (65%) of [(C5 (CH3) s) (C5H4) C (CH3) z ~ TiCl]. 1H-NMR: (C6D6, 300 MHZ): 5 = 1.16 (s, 3H, C (CH3) 2), 1.70 (s, 15H, C5 (CH3) 5), 1.75 (s, 3H , C (CH3) 2), 3.43 / 4.65 / 6.03 / 6.70 (s, lH, C5H4). 13 C-NMR: (C6D6, 75 MHz): d = 12, 82 (C5 (CH3) 5), 22.76 / 24.50 (C (CH3) 2), 108, 10 (C (CH3) 2) 117 , 23 / 117.46 / 120.04 / 124.09 (C4H4), 122, 55 (C5 (CH3) 5), 132, 16 (ipso-C).

Example 3: Synthesis of fulvene complex by reaction of 6,6-dimethylfulvene with Cp * ZrCl 3 in the presence of magnesium [(Cs (CH 3) 5) (C 5 H) C (CH 3) 2 ZrCl]. CP * ZrCl3 (0.380 g, 1.14 mmol) and 1.1 equivalents of magnesium, 0.031 g, 1.26 mmol) were placed in 10 mL of THF. To this solution were added, dropwise, 1.1 equivalents of 6,6-dimethyl fulvene (0.134 g, 126 mmol). After 5 minutes, a turbidity of the reaction solution occurred. It was stirred overnight to completely dissolve the magnesium. It was concentrated by evaporation in HV to dryness, taken up in 10 ml of hexane and the formed precipitate was filtered off. From the filtrate, 197 mg (47%) of [(C5 (CH3) 5) (C5H4) C (CH3) 2ZrCl] was isolated as a reddish brown solid product. XH-NMR: (C6D6, 300 MHZ): d = 1.77 (s, 15H, C5 (CH3) 5), 1, 98, 1, 99 (s, 3H, C (CH3) 2), 5.40 (dd, 1H, 3 J (H, H) = 2, 69, 3.02 Hz, C5H4), 5.58 (dd, ÍH, 3J (H, H) = 2, 69, 2, 68 Hz, C5H4), 5.85 ( dd, 1H, 3J (H, H) = 2.68, 3.02 Hz, C5H4), 5.92 (dd, 1H, 3J = 2.69, 2.68 Hz, C5H4) ppm. 13 C-NMR: (C6D6, 75 MHz): d = 10.98 (C5 (CH3) 5), 21.35, 21.90 (C (CH3) 2), 109.78 (C (CH3) 2), 107.75, 110.68, 113.88, 118.11 (C5 (H4), 115.69 (ipso-C5H4), 122, 35 (C (CH3) 5) ppm. MS (70eV) m / e (%): 366 (10) [M +], 330 (5) [M + -HC1], 259 (2), 135 (5) [Cp *], 106 (100) [dimet ilf ulveno].

Example 4. Synthesis of bis (α6,6,6-diphenyl fulvene) titanium by reaction of 6,6-diphenyl fulvene with titanium tetrachloride in the presence of magnesium. 610 mg (1.83 mmol) of TiCl4 (THF), 89 mg (3.65 mmol) of magnesium filings and 841 mg (3.65 mmol) of 6,6-diphenylfulvene in a Schlenk vessel were combined in a Schlenk vessel. ml of THF as reaction medium. To complete the reaction, it was stirred for 12 hours until complete consumption of the magnesium filings. Concentration by evaporation of the reaction solution to dryness gave a green solid product which could be separated from the magnesium chloride formed by collecting n-hexane and filtration. By stepped evaporation and cooling the filtrate, 640 mg (70%) of bis (? 6-6,6-diphenylthiovan) titanium was obtained.

Use 5. Synthesis of the fulvene complex by reaction of 6,6-dimethyl ulvene with CpTiCl 3, in the presence of magnesium [(C5H5) (C5H4) C (CH3) 2TiCl]. They were placed in 20 ml of THF, CpTiCl3 (0.410 g, 1.87 mmol) and 1.05 equivalents of magnesium (0.048 g, 1.96 mmol). To this yellow solution were added dropwise at RT 1.03 equivalents of 6,6-dimethyl fulvene (0.204 g, 1.92 mmol) and stirred until the magnesium used had been consumed. It was then concentrated by evaporation in HV and the resulting green solid product was taken up in 20 ml of hexane. After separation by filtration of the solid product, the solution, dark green in color, was evaporated to one half in HV. By crystallization at -20 ° C, 0.2 g (42%) of [(C5H5) (C5H4) C (CH3) 2TiCl] was obtained as a dark green solid product. 1H-NMR: (C6D6, 300 MHz): d = 0.94, 1.64 (s, 3H, C (CH3) 2) • 3.66 (m, 1H, C5H4), 4.76 (m, 1H, C5H4), 5.80 s, 5H, CSH5), 6.23 (m, 1H, C5H4), 6.66 (m, 1H, C5H4) ppm 13C-NMR: (C6D6, 75 MHz): d = 10.98 (C5 (CH3) 5), 21 , 35 21.90 (C (CH3) 2), 109.78 (C (CH3) 2), 107.75, 110.68, 113.88, 118.11 (C5H4), 115.69 (ipso-C5H4), 122.35 (C5 (CH3) 5) ppm Example 6 Synthesis of fulvene complex by reaction of 6,6-diphenyl ulvene with CP * TiCl 3 in the presence of magnesium [(C5 (CH3) 5) (C5H4) C (C6H5) 2TiCl]. Cp * TiCl3 (0.690 g, 2.38 mmol) and 1.1 equivalents of magnesium (0.064 g, 2.62 mmol) were placed in 20 mL of THF. To this solution were added, drop by drop, at RT, 1.1 equivalents of 6,6-diphenyl fulvene (0.604 g, 2.62 mmol). It was stirred overnight at RT in such a manner that all the magnesium was consumed. The solvent in HV was removed and the green residue was taken up in hexane. The precipitate was separated by filtration and the solution was concentrated by evaporation to half. For the separation by crystallization, the charge was cooled to -20 ° C, whereby 0.29 g (27%) of [(C5 (CH3) 5 (C5H4) C (C6H5) 2TiCl] as a solid product was obtained green, 1H-NMR: (C6D6, 300 MHz): d = 1.55 (s, 15 H, C5 (CH3) 5), 4.20, 4.55, 5.89, 6.37 (m, 1H) , C5H4), 6.89-7.41 (m, 10H, C6H5) ppm 13C-NMR: (C6D6, 75 MHz): d = 12.38 (C5 (CH3) 5), 116.29, 117, 24, 118.22, 121.82 (C4H4), 124.04 (C5 (CH3) 5), 125.61 (ipso-C5H4), 126.50, 126.84, 127.26, 128.07, 128 , 83, 129.81 (C6H5), 130.72 (-C -CβHj-)), 141.93, 144.23 (ipso-C6H5) ppm. MS (70eV) m / e (%): 448 (5) [M +], 413 (2) [M + -HC1], 230 (100) [6,6-diphenylfulvene], 135 (15) [Cp *], 78 (12) [Ph].

Example 7. Synthesis of the fulvene complex by reaction of 6,6-diphenyl fulvene with CP * ZrCl 3 in the presence of magnesium [(C 5 (CH 3) 5) (C 5 H 4) C (C 6 H 5) 2 ZrCl].

C? * ZrCl3 (0.310 g, 093 mmol and 1.05 equivalents of magnesium (0.024 g, 0.98 mmol) in 10 ml of THF was added to this solution, 1.05 equivalents of 6 were added dropwise, 6-diphenylfulvene (0.225 g, 0.98 mmol), stirred overnight to completely convert magnesium, concentrated by evaporation in HV to dryness, it was taken up in 20 ml of toluene and the insoluble precipitate was filtered off. After coating with hexane at -20 ° C, 178 mg (39%) of [(C5 (CH3) 5) (C5H4) C (C6H5) 2ZrCl] was obtained as a red solid product. ^ • H-NMR: (C6D6, 300 MHZ): d = 1.63 (s, 15 H, C5 (CH3) 5), 4.65, 5.20, 5.22, 6.06 (m, 1H) , C5H4), 6.98-7.16 (m, 8H, C6 (H5), 7.26-7.49 (m, 2H, C6H5) ppm 13C-NMR: (C6D6, 75 MHz): d = 11.66 (C5 (CH3) 5), 104.67, 111.14, 113.62, 117.52 (C4H4), 120, 82 { C5 (CH3) 5),. 125, 61 (ipso-C5H), 126.50, 126.84, 127.26, 128.07, 128 83, 129.81 (C6H5), 130.72 (-C (C6H5)), 141.93, 144.23 (ipso-C6H5) ppm. MS (70eV) m / e (%): 448 (5) [M +], 413 (2) [M + -HC1], 230 (100) [6,6-difenilfulvene], 135 (15) [Cp *], 78 (12) [Ph].

Example 8. Synthesis of the fulvene complex by reaction of 2, 3, 4, 5-tetramethylfulvene with CP * TiCl3 in the presence of magnesium [(C5 (CH3) 5) (C5 (CH3) 4) CH2TiCl]. Cp * TiCl3 (0.370 g, 1. 28 mmoles) and 1.05 equivalents of magnesium (0.033 g, 1.35 mmoles) in 25 ml of THF. To this red solution was added, dropwise, at room temperature, 1.05 equivalents of 2,3,4,5 tetramethylfulvene (0.185 g, 1.35 mmol). It was stirred overnight at RT so that all the magnesium was consumed. The solvent was removed in HV and then the green residue in hexane was collected. The solid product was separated by filtration and the solution was concentrated by evaporation to half. For the separation by crystallization, the charge was cooled to -20 ° C, whereby 0.23 g (52%) of [(C5 (CH3) 5) (C5 (CH3) 4) CH2TiCl] as product was obtained solid green. XH-NMR: (C6D6, 300 MHz): d = 1.21, 1.47, 1.70 (s, 3H, C5 (CH3) 4 = CH2), 1.79 (s, 3H, C5 (CH3) 5), 2.07 (s, 3H, C5 (CH3) 4 = CH2), 1.43 (d, ÍH, 2J (H, H) = 3.66 Hz, C5 (CH3) 4 = CHH), 2.54 (d, ÍH, 2J (H, H), 3.66 Hz, C5 (CH3) 4 = CHH) ppm. 13 C-NMR: (C6D6, 75 MHz): d * = 9.82, 10.22 (C5 (CH3) 4 = CH2), 11.13 (C5 (CH3) 5). 11.85 14.00 (C5 (CH3) 4 = CH2), 77.65 (C5 (CH3) 4 = CH2), 120.08 (C5 (CH3) 5), 120.32, 124.43 124.73, 128.61, 135.17 (C5 (CH3) 4 = CH2) 4 = CH2) ppm.

Example 9 Synthesis of the fulvene complex by reaction of 2,3,4,5-tetramethylfulvene with CpTiCl 3 in the presence of magnesium [(C5H5) (C5 (CH3) 4) CH2TiCl]. They were placed in 20 ml of THF, CpTiCl3 (0.350 g, 1.60 mmol) and 1.05 equivalents of magnesium (0.041 g, 1.67 mmol). To this solution, 1.1 equivalents of 2, 3, 4, 5-tetramethylfulvene (0.260 g, 1.67 mmol) were added dropwise at room temperature and stirred until the magnesium used was consumed. It was then concentrated by evaporation in HV and the resulting green solid product was taken up in 20 ml of hexane. After separation by filtration of the solid product, the dark green solution was concentrated by evaporation to half in HV. Crystallization at -20 ° C yielded 0.3 g (67%) of [(C5H5) (C5 (CH3) 4) CH2TiCl] solid product of dark green color. 1H-NMR: (C6D6, 300 MHZ): d = 0.82, 1.27, 1.74 (s, 3H, C5 (CH3) 4 = CH2), 1.99 (d, 1H, 2J (H, H) = 3.7 Hz, C5 (CH3) 4 = CHH), 2.05 (s, 3H, C5 (CH3) 4 = CH2), 2.56 (d, ÍH, 2J (H, H) = 3.7 Hz, C5 (CH3) 4 = CHH), 5.77 (s, 5H, C5H5) ppm. 13 C-NMR: (C6D6, 75 MHZ): d = 9.47, 10.35, 12.01.1 12.95 (C5 (CH3) 4 = CH2), 74.47 (C5 (CH3) 4 = CH2), 110.80 (C5H5), 119.92, 124.60, 127.82, 129.43, 134.80 (C5 (CH3) 4 = CH2) ppm. MS (70eV) m / e (%): 283 (10) [M +], 247 (15) [M + -HC1], 134 (50) [2, 3, 4, 5-tetramethylfulvene], 119 (100) [2, 3, 4, 5-tetramethylfulvene-CH4], 65 (30) [Cp].

Example 10. Synthesis of the fulvene complex by reaction of 1,2,3,4,6-pentamethylfulvene with CpTiCl 3 in the presence of magnesium [(C 5 H 5) (C 5 (CH 3) 4) C (H) (CH 3) TiCl].

CpTiCl3 (0.450 g, 2.05 mmol) and 1.05 equivalents of magnesium (0.054 g, 2.15 mmol) were placed in 20 ml of THF. To this solution, 1.03 equivalents of 1, 2, 3, 4, 6-pentamethylfulvene (0.320 g, 2.15 mmol) were added dropwise at RT and stirred until the magnesium used had been consumed. It was then concentrated by evaporation in HV and the resulting green solid product was taken up in 20 ml of hexane. After evaporation by filtration of the solid product, the solution, dark green in color, was evaporated to one half in HV. Crystallization at -20 ° C gave 0.17 g (28%) of [(C5H5) (C5 (CH3) 4) C (H) (CH3) TiCl] as a dark green solid product. XH-NMR: (C6D6, 300 MHz): d = 0.73, 1.12 (s, 3H, C5 (CH3) 4 = C (CH3) (H), 1.64 (d, 3H, 3J (H , H) = 7.25 Hz, C5 (CH3) 4 = C (CH3) (H)), 1.71 (s, 3H, C5 (CH3) 4 = C (CH3) (H)), 2.29 (q, ÍH, 3J (H, H) = 7.25 Hz, C5 (CH3) 4 = C (CH3) (H)), 2.55 (s, 3H, C5 (CH3) 4 = C (CH3) (H)), 5.79 (s, 5H, C5H5) ppm 13C-NMR: (C6D6,) 75 MHz): d = 10.87, 13.35, 16.19, 16.97 (C5 (CH3 ) 4 = C (CH3) (H)), 37.62 (C5 (CH3) 4 C (CH3) (H)), 94.39 (C5 (CH3) 4 = C (CH3) (H)), 112 , 02 (C5H5), 121.46, 125.56, 130.91, 131.46, 136.90 (C5 (CH3) 4 = C (CH3) (H)) ppm.

Example 11. Synthesis of the fulvene complex by reaction of 6-tert-butylfulvene with Cp * TiCl3 in the presence of magnesium [C5 (CH3) 5) (C5H4) C (H) (C (CH3) 3) TiCl]. Cp * TiCl3 (0.450 g, 1.55 mmol) and 1.05 equivalents of magnesium (0.039 g, 1.63 mmol) were placed in 15 mL of THF. To this solution, 1.05 equivalents of tert-butylfulvene (0.249 g, 1.63 mmol) were added dropwise at RT. It was stirred overnight at RT so that all the magnesium was consumed. The solvent was removed in HV and the green residue was taken up in hexane. The solid product was separated by filtration and the solution was concentrated by evaporation to half. For the recrystallization separation, the charge was cooled to -20 ° C, whereby 0.35 g (64%) of [(C5 (CH3) 5) (C5H4) C (H) (C (CH3) was obtained. 3) TiCl] in the form of green crystals. An analysis of the structure was carried out by means of X-rays (figure 1). from: > 98% lH-NMR: (C6D6, 300 MHz): d = 1.16 (s, 9H, C5H4 = C (H) (C (CH3) 3)). 1.68 (s, 1H, C5H4 = C (H) (C (CH3) 3)), 1.70 (s, 15H, C5 (CH3) 5), 3.15, 4.74, 5.97, 6.63 (m, 1H, C 5 H 4 = C (H) (C (CH 3) 3)) ppm. 13C-NMR: (C6D6,) 75 MHz): d = 11.69 (C5 (CH3) 5), 32.30 (C5H4 = C (H) C (CH3) 3)), 34.28) (C5H4 = C (H) (C (CH3) 3)), 114.31 (C5H4 = C (H) (C (CH3) 3)), 117.83, 118.31, 118.77 (C5H4) = C (H ) (C (CH3) 3)), 120.46 C5 (CH3) 5), 124.72, 128.23 (C5H4 = C (H) C (CH3) 3)) ppm. MS (70eV) m / e (%): 353 (12) [M +], 316 (5) [M + -HC1], 270 (18), 235 (8), 135 (100) [Cp *], 119 ( 35), 80 (85), 57 (90) [C (CH3) 3].

Example 12 Synthesis of the fulvene complex by reaction of 6-tert-butylfulvene with CpTiCl3 in the presence of magnesium [(C5H5) (C5H4) C (H) (C (CH3) 3) TiCl]. They were placed in 120 ml of THF, CpTiCl3 (0.420 g, 1.91 mmol) and 1.05 equivalents of magnesium, (0.048 g, 2.01 mmol). To this solution, 1.03 equivalents of tert-butylfulvene (0.295, 1.91 mmol) were added dropwise at RT and stirred until the magnesium used had been consumed. It was then concentrated by evaporation in HV and the resulting green solid product was taken up in 20 ml of hexane. After separation by filtration of the solid product, the dark green solution was evaporated by half evaporation in HV. By crystallization at -20 ° C 0.23 g (44%) of ((C5H5) (C5H4) C (H) (C (CH3) 3) TiCl] were obtained as dark green crystals. of > 98%. - H-NMR: (C6D6, 300 MHz): d = 1.05 (s, 9H, C5H4 - = C (H) (C (CH3) 5)), 2.05 (s, ÍH, C5H4 = C (H) (C (CH3) 3)), 3.28, 4.83 (m, ÍH, C5H4 = C (H) (C (CH3) 3)),), .85 (s, 5H, C5H5), 6.17, 6.59 (m, ÍH, C5H4 C (H) (C (CH3) 3)) ppm. 13C-NMR: (C6D6, 75 MHz): d = 32.84 (C5H4 C (H) (C (CH3) 3)), 35.76 (C5H4 = C (H) (C (CH3) 3)), 111.23 (C5H5), 111.63 (C5H4 = C (H) (C (CH3) 3)). 116, 62, 117.41, 121.63, 127.65, 127.50 (C5H4 = C (H) (C (CH3) 3)), ppm. MS (70eV) m / e (%): 282 (5) [M +], 246 (45) [M + -HC1], 228 (15), 135 (10) [Cp *], 119 (35).

Examples of polymerization. Example 13. Obtaining the catalyst solution. 8.3 mg (22.6 μmol) of [(CP *) (C5H4 = C (CH3) 2) ZrCl of example 3 was dissolved in 11.3 ml of toluene.

Polymerization of ethylene. 100 ml of toluene were placed in a 250 ml glass reactor, 1 ml of a 0.1 molar solution of triisobutylaluminium in toluene and 0.5 ml of the catalyst solution were added. The ethylene was then introduced into the solution with a tube for the introduction of gases, continuously, at a pressure of 1.1 bar Polymerization was initiated by the addition of 1 ml of a 0.001 molar solution of tetrakis (pentafluorophenyl) ) N, N-dimethyl anilinium borate in toluene After a polymerization time of 5 minutes at a temperature of 40 ° C and an ethylene pressure of 1.1 bar, the reaction was stopped by the addition of 10 ml. of methanol, the formed polymer was separated by filtration, washed with acetone and dried in the vacuum drying cabinet, 1.61 g of polyethylene was obtained.

Example 14. Copolymerization of ethylene and propylene. 500 ml of toluene and 5 ml of a 10% solution of MAO in toluene were placed in a 1.4 liter steel autoclave, which was equipped with a mechanical stirrer, pressure gauge, temperature sensor, a device for control of the temperature, a lock for the catalyst and a dosing device of the monomers for ethylene and propylene and were stirred for 10 minutes. Then, 52 g of propylene were metered in. The internal temperature was adjusted to 40 ° C with a thermostat. Ethylene was then metered in until the internal pressure of the reactor was 6 bar. By addition of 5 ml of the catalyst solution of example 5 the polymerization was started and ethylene was dosed continuously so that the internal pressure, at 40 ° C, was kept constant at 6 bar. After 1 hour of polymerization time, the polymerization was stopped with a 1% solution of HCl in methanol, stirred for 10 minutes and then the polymer was precipitated in methanol. The polymer, obtained in this way, was washed with methanol, isolated and dried for 20 hours at 60 ° C under vacuum, whereby 48 g of copolymer was obtained. The determination by IR spectroscopy of the composition of the copolymer gave a constitution of 82.9% ethylene and 17.1% propylene. A Tg of -24 ° C was determined with the DSC method.

Example 15. Obtaining the catalyst 73.9 mg (0.221 mmol) of TiCl4 (THF) 2 were dissolved in 3 ml of THF. Then, 5.4 mg (0.22 mmol) of magnesium and 51 mg (0.221 mmol) of 6,6-diphenylfulvene were added. After 20 hours of stirring at 20 ° C a dark green solution was obtained. The solution was concentrated by evaporation to dryness, the formed residue was dried for 2 hours in HV and then combined with 22 ml of toluene, whereby a dark green suspension was formed. In this case 1 ml of the catalyst suspension contained 0.012 mmole of titanium.

Polymerization of ethylene. 90 ml of toluene and 5 ml of an MAO solution (10% in toluene) were placed in a 250 ml glass reactor and stirred for 5 minutes. Then 5 ml of the catalyst suspension was added and stirred for 10 minutes at 40 ° C. It was then introduced, continuously, into the ethylene solution with a tube for the introduction of gases. After 10 minutes of polymerization time at a temperature of 40 ° C and an ethylene pressure of 1.1 bar, the reaction was stopped by the addition of 10 ml of a 10% solution of HCl in methanol, the polymer formed it was separated by filtration, washed with methanol and dried in the vacuum drying cabinet. 8.9 g of polyethylene were obtained.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, property is claimed as contained in the following:

Claims (8)

R E I V I N D I C A C I O N S

1. - Procedure for obtaining fulvene metal complexes of the formula (la) XpM (the). or of the formula (Ib) ApXpU (Ib). characterized in that M means a metal of the groups IHb, IVb, Vb, VIb or of the lanthanides or of the actinides of the Periodic Table of the Elements according to IUPAC, A means an anionic ligand where one or several times bridged, X means hydrogen is an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, an alkylaryl group with 7 to 40 carbon atoms, an arylalkenyl group with 8 to 40 carbon atoms, a silyl group substituted by a hydrocarbon radical having 1 to 10 carbon atoms, a halogen atom or an amide of the formula NR72, L means a neutral ligand, R1, R2, R3 R4, R5, R6 are the same or different and mean hydrogen, halogen, a cyano group, an alkyl group with 1 to 20 carbon atoms, a group fluoroalkyl with 1 to 6 carbon atoms, a fluoroaryl group with 6 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an aryl group with 6 to 20 carbon atoms, an aryloxy group with 6 to 10 atoms of carbon, an alkenyl group with 2 to 10 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, an alkylaryl group with 7 to 40 carbon atoms, an arylalkenyl group with 8 to 40 carbon atoms, an alkynyl group with 2 to 10 atoms carbon atoms, a silyl group substituted by hydrocarbon radicals with 1 to 10 carbon atoms, an amino group optionally substituted by hydrocarbon radicals with 1 to 20 carbon atoms, or R 1, R 2, R 3, R 4, R 5, R 6 respectively, together with the atoms with which they are linked, one or more aliphatic or aromatic ring systems, which may contain one or more heteroatoms (O, N, S) and having from 5 to 10 carbon atoms, R7 means hydrogen, alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, an alkylaryl group with 7 to 40 carbon atoms, a silyl group substituted for hydrocarbon radicals with 1 to 10 carbon atoms, an amino group optionally substituted by hydrocarbon radicals having 1 to 20 carbon atoms, m, p means the numbers 0, 1, 2, 3 or 4, which are produced by the valency and by the state of linked to M, as well as k means the numbers 1, 2 or 3, and the sum k + m + p amounts to 1 to 5 as a function of the degree of oxidation of M, n means a number from 1 to 10, characterized in that it comprises the reaction of a transition metal compound of the formula (Ha) or (Hb) AmXsM (lia) AmXsLnM (I Ib) wherein A, X, L, M, m, s and n have the meaning indicated above and s means 2, 3, 4, 5 or 6 and s > p, with a fulvene compound of the formula (III) wherein R1, R2, R3, R4, R5 and R6 have the meaning indicated above, in the presence of a reducing agent.

2. - Process according to claim 1, characterized in that the reaction is carried out in a suitable reaction medium at temperatures of -100 to + 250 ° C.

3. Process according to claim 1, characterized in that alkali metals, alkaline earth metals or lithium alkyls are used as reducing agents.

4. Process according to claim 1, characterized in that the reaction is carried out in a solvent.

5. Process according to claim 4, characterized in that the reaction is carried out in an ether.

6.- Metallic complexes of fulvene of the formula (la) or (Ib), characterized in that M means a metal of the group formed by titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium, k means 1, A, X, L, m, n, p, R1, R2, R3, R4, R5 and R6 have the meaning indicated above, with the exception of the compounds of the formula (la) or (Ib), in which R1 and R2 mean hydrogen and , simultaneously, R3, R ^ R-R * means a methyl group simultaneously A means a pentamethylcyclopentadienyl group or a carbohydrate group of the formula C2B9Hn.

7. Catalytic system, consisting of a) a fulvene metallic complex of the formula (la) or (Ib), prepared according to the process of the invention, wherein M means a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium , tantalum and chromium, k means 1, A, X, L, m, n, p, Rx. R2, R3, R4, R5 and R6 have the meaning indicated above and b) a co-catalyst suitable for the activation of the metal complex a) the molar ratio between component a) and component b) being in the range of 1: 0 , 1 to 1: 10,000.

8. Use of the catalytic system according to claim 7 for the polymerization of olefins and / or dienes.