Metallocene complexes with cationic bridges

Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing

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556 1, 556 21, 556 22, 556 23, 556 30, 556 41, 556 47, 556 53, 556 54, 556 56, 556 58, 556351, 556352, 556943, 526127, 526160, 526170, 526172, 502103, 502117, 502152, 534 15, 564281, 568 9, C07F 1700, C07F 900, C07F 708, C08F 4642

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058832777

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BRIEF SUMMARY
This application was filed as a request for U.S. examination under 35 U.S.C. .sctn.371 of International application No. PCT/EP96/00619 filed Feb. 14, 1996.
The present invention relates to metallocene complexes of the formula I ##STR3## where the substituents have the following meanings: M is a metal of transition group III, IV, V or VI of the Periodic Table of the Elements or a metal of the lanthanide group, -alkyl, C.sub.6 -C.sub.15 -aryl or --OR.sup.5, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, cycloalkyl which may in turn bear C.sub.1 -C.sub.10 -alkyls as substituents, C.sub.6 -C.sub.15 -aryl or arylalkyl, where two adjacent radicals may also together form a cyclic group having from 4 to 15 carbon atoms, or Si(R.sup.10).sub.3 where -C.sub.10 -cycloalkyl, -C.sub.10 -cycloalkyl or C.sub.6 -C.sub.15 -aryl, alkoxide.
The present invention further relates to ligand systems of the formula II ##STR4## and also processes for preparing such metallocene complexes I and ligand systems II, the use of the ligand systems II for preparing the metallocene complexes I and to the use of the metallocene complexes I as catalysts for the polymerization of alkanes.
Bridged metallocene complexes in which elements of main group IV of the Periodic Table of the Elements function as a bridge are known, for example from EP-A 344 887 and are used as catalysts for the polymerization of alkenes.
However, the bridge is here restricted to neutral bridge atoms without the possibility of subsequent functionalization directly on the bridging atom. Furthermore, it is not possible to electronically influence the ligand system by introduction of a charge directly in the bridge.
G. K. Anderson et al., Organometallics 7 (1988), 2285-2288 discloses the introduction of phosphorus as bridging element between two cyclopentadienyl ligands. Ch. Qian et al., J. Chem. Soc. Dalton Trans. (1993), 3441-3445 and Ch. Qian et al., J. Organomet. Chem. 445 (1993), 79-84 describe nitrogen as a bridge in metallocene complexes. However, this has the disadvantage that the bridging element interacts with the metal of the metallocene complex or with other coordinatively unsaturated substrates.
It is an object of the present invention to provide metallocene complexes which do not have the disadvantages mentioned and which make possible, in particular, a very variable structure and possibly functionalization directly on the bridging atom.
We have found that this object is achieved by the metallocene complexes I defined in the introduction.
In addition, the present invention provides ligand systems II and also processes for preparing such metallocene complexes I and ligand systems II, and provides for the use of the ligand systems II for preparing the metallocene complexes I and the use of the metallocene complexes I as catalysts for the polymerization of alkenes.
Among the novel metallocene complexes of the formula I ##STR5## preference is given to those in which the substituents have the following meaning: viz. titanium, zirconium or hafnium, or a metal of the lanthanide group, but in particular zirconium or hafnium, particular C.sub.1 -C.sub.4 -alkyl, where in the case of a plurality of radicals X these can also be different, -alkyl, C.sub.6 -C.sub.15 -aryl, in particular linear or branched C.sub.1 -C.sub.6 -alkyl, or two adjacent radicals can together form a cyclic group having from 4 to 12 carbon atoms, -C.sub.15 -aryl, in particular linear or branched C.sub.1 -C.sub.4 -alkyl, and the two radicals R.sup.11 and R.sup.12 are preferably identical.
Particular preference is given to metallocene complexes I which have a symmetric structure, ie. R.sup.1 and R.sup.6, R.sup.2 and R.sup.7, R.sup.3 and R.sup.8 as well as R.sup.4 and R.sup.9 are in each case identical.
The anion Z.sup.- can in principle be selected without restriction. Anions which have been found to be particularly useful are halides, in particular iodide, carboxylates, in particular halogenat

REFERENCES:
G. K. Anderson et al., Organometallics 7, 1988, pp. 2285-2288.
Ch. Quian et al., J. Chem. Soc. Dalton Trans, 1993, pp. 3441-3445.
Ch. Quian et al., J. Organomet. Che. 445, 1993, pp. 79-84.
Monatshefte fur Chemie 144, 243-247 (1983).

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