86954-94-1Relevant articles and documents
Reactions of vinylzirconocene complexes with a zirconium hydride. The unexpected formation of [μ-(β-η1:α,β-η 2-styryl)](μ-chloro)bis[bis(η 5-cyclopentadienyl)-zirconium], a binuclear (olefin)zirconocene complex
Erker, Gerhard,Kropp, Kurt,Atwood, Jerry L.,Hunter, William E.
, p. 1555 - 1561 (2008/10/08)
(μ-Ethylene)bis(zirconocene chloride) (1a) is formed rapidly in nearly quantitative yield upon hydrozirconation of vinylzirconocene chloride, 5a. In contrast, the slow reaction of (β-styryl)zirconocene chloride (5d) with oligomeric hydridozirconocene chloride (4) gives an equimolar mixture of Cp2ZrCl2 (6), Cp2ZrCl(CH2CH2Ph) (7), and the novel binuclear (olefin)zirconocene complex Cp2ZrCl(CH=CHPh)ZrCp2 (8). The latter crystallizes in space group P21/n with cell constants a = 8.380 (4) A?, b = 22.256 (9) A?, c = 12.667 (6) A?, and β = 97.40 (3)°. The molecular structure of 8 is characterized by an almost planar bridging olefinic ligand. The Zr(1)-C(1) σ bond is short (2.196 (7) A?). Zr-C bond distances of 2.440 (7) and 2.462 (7) A?, are found for the Zr(2)-(η2-alkenyl) moiety. The chemistry of 8 is dominated by the reactive Zr-C σ bond. Carbon monoxide is rapidly inserted with preservation of a binuclear structure to form 14. Reactions with protic reagents point to the formation of mononuclear (η2-styrene)zirconocene as a reactive intermediate.