Anorganische Chemie - Beckhaus

Synthesis of semibridging m-vinylidene Titanium-Copper and -Gold Complexes. Crystal and Molecular Structure of Cp*2Ti(Cl)(µ-C=CH2)AuPPh3

R. Beckhaus, J. Oster, R. Wang, U. Böhme
Organometallics 1998, 17, 2215 - 2221.

The titanocenevinylidene intermediate [Cp*2Ti=C=CH2] (1) (Cp*: C5(CH3)5), formed by methane elimination from Cp*2Ti(CH=CH2)(CH3) (2), reacts with group 12 LM'X complexes ([Me3PCuCl]4 (4a), [Ph3PCuCl]4 (4b), [i-Pr3PCuCl]4 (4c), [Me3PCuCCPh]4 (4d), [Ph3PAuCl] (4e) (Ti:M' = 1:1), to give heterodinuclear µ-vinylidene compounds Cp*2Ti(X)(μ-C=CH2)M'L (5a-5e). The molecular structure of 5e was determined by X-ray diffraction analysis, which revealed a titanium gold bond asymmetrically bridged by the vinylidene ligand. A semi-bridging bonding mode for the C=CH2-group in the new complexes is indicated by NMR spectroscopic and X-ray diffraction data.