Method for producing metallocene compounds formed by two carbanions

A process for preparing metallocene compounds of the formula

• wherein
• CpI and CpII are two identical or different carbanions having a cyclopentadienyl-containing structure in which from one to all H atoms can be replaced by identical or different radicals selected from the group consisting of linear or branched C1-C20-alkyl which may be monosubstituted to fully substituted by halogen, monosubstituted to trisubstituted by phenyl or monosubstituted to trisubstituted by vinyl;
• C6-C12-aryl;
• halogenoaryl having from 6 to 12 carbon atoms;
• and which may be monosubstituted or disubstituted by D and A,
• D is a donor atom which can additionally bear substituents and which, in its respective bonding state, has at least one free electron pair,
• A is an acceptor atom which can additionally bear substituents and which, in its respective bonding state, has at least one electron pair vacancy,
• wherein D and A are linked by a reversible coordinative bond in such a way that the donor group takes on a positive charge and the acceptor group takes on a negative charge,
• M represents a transition metal of transition group III, IV, V or VI of the Periodic Table of the Elements including the lanthanides and actinides,
• X is one anion equivalent and
• n is, depending on the charge of M, zero, one, two, three or four,
• which comprises reacting with one another
• one compound each of the formulae (II) and (III)
• or one compound each of the formulae (IV) and (V)
• or one compound each of the formulae (VI) and (VII)
• with elimination of M′X in the presence of an aprotic solvent or one compound each of the formulae (VIII) and (III)
• or one compound each of the formulae (IV) and (IX)
• or one compound each of the formulae (X) and (VII)
• with elimination of E(R1R2R3)X and F(R4R5R6) in the absence or in the presence of an aprotic solvent, where
• CpIII, CpIV are two identical or different uncharged molecule parts having a cyclopentadiene-containing structure, but otherwise the same as CpI and CpII,
• M′ is one cation equivalent of an alkali or alkaline earth metal or Tl,
• E and F are, independently of one another, one of the elements Si, Ge or Sn and
• R1, R2, R3, R4, R5 and R6 are, independently of one another, straight-chain or branched C1-C20-alkyl, C6-C12-aryl, C1-C6-alkyl-C6-C122-aryl, C6-C12-aryl-C1-C6-alkyl, vinyl, allyl or halogen,
• where, furthermore, in the formulae (VIII), (IX) and (X) hydrogen can be present in place of E(R1R2R3) and F(R1R2R3) and in this case X can also represent an amide anion of the type R2N⊖ or a carbanion of the type R3C⊖ or an alkoxide anion of the type RO⊖, and where it is furthermore possible to react compounds of the formula (II) or (VIII) in the presence of compounds of the formula (V) or (IX) directly with a transition metal compound of the formula (VII).

A rearrangement product of a metallocene compound of the formula

• where
• CpI and CpII are two identical or different carbanions having a cyclopent-adienyl-containing structure in which from one to all H atoms can be replaced by identical or different radicals selected from the group consisting of linear or branched C1-C20-alkyl which may be monosubstituted to fully substituted by halogen, monosubstituted to trisubstituted by phenyl or monosubstituted to trisubstituted by vinyl;
• C6-C12-aryl;
• halogenoaryl having from 6 to 12 carbon atoms and organometallic substituents such as silyl, trimethylsilyl and ferrocenyl;
• and which may be monosubstituted or disubstituted by D and A,
• D is a donor atom which can additionally bear substituents and which, in its respective bonding state, has at least one free electron pair,
• A is an acceptor atom which can additionally bear substituents and which, in its respective bonding state, has at least one electron pair vacancy,
• where D and A are linked by a reversible coordinative bond in such a way that the donor group takes on a positive (partial) charge and the acceptor group takes on a negative (partial) charge,
• M represents a transition metal of transition group III, IV, V or VI of the Periodic Table of the Elements (Mendeleev) including the lanthanides and actinides,
• X is one anion equivalent and
• n is, depending on the charge of Me zero, one, two, three or four, with self-activation in which after opening of the D/A bond the acceptor atom A binds to an X ligand to form a zwitterionic metallocene complex structure generating a positive charge on the transition metal M and a negative charge on the acceptor atom A, where a further X ligand is H or substituted or unsubstituted C into whose bond to the transition metal M the olefin insertion for polymerization occurs and where preferably 2 X ligands are linked to one chelating ligand.

A reaction product of ionizing agents with a metallocene catalyst, said reaction product having the formula:

• wherein
• CpI and CpII are two identical or different carbanions having a cyclopentadienyl-containing structure in which from one to all H atoms can be replaced by identical or different radicals selected from the group consisting of linear or branched C1-C20-alkyl which may be monosubstituted to fully substituted by halogen, monosubstituted to trisubstituted by phenyl or monosubstituted to trisubstituted by vinyl;
• C6-C12-aryl;
• halogenoaryl having from 6 to 12 carbon atoms;
• and which may be monosubstituted or disubstituted by D and A,
• D is a donor atom which can additionally bear substituents and which, in its respective bonding state, has at least one free electron pair,
• A is an acceptor atom which can additionally bear substituents and which, in its respective bonding state, has at least one electron pair vacancy,
• Wherein D and A are linked by a reversible coordinative bond in such a way that the donor group takes on a positive charge and the acceptor groups takes on a negative charge,
• M represents a transition metal of transition group III, IV, V or VI of the Periodic Table of the Elements including the lanthanides and actinides,
• X is one anion equivalent and
• n is, depending on the charge of M, zero, one, two, three, or four,
• Base represents a Lewis base, and
• Anion represents the overall bulky anion which does not coordinate readily.