1094077-59-4Relevant articles and documents
Alkylaluminum-complexed zirconocene hydrides: Identification of hydride-bridged species by NMR spectroscopy
Baldwin, Steven M.,Bereaw, John E.,Brintzinger, Hans H.
, p. 17423 - 17433 (2009/06/08)
Reactions of unbridged zirconocene dichlorides, (RnC 5H5-n)2ZrCl2 (n=0, 1, or 2), with diisobutylaluminum hydride (HAI'Bu2) result in the formation of tetranuclear trihydride clusters of the type (RnC5H 5-n)2Zr(μ-H)3(Al iBu2)3(μ-CI) 2, which contain three [Al iBu2] units. Ring-bridged ansa-zirconocene dichlorides, Me2E(RnC5H 4-n)2ZrCl2 with E=C or Si, on the other hand, are found to form binuclear dihydride complexes of the type Me2E(R nC5H4-n)2Zr(CI)(μ-H) 2Al iBu2 with only one [AIBu2] unit. The dichotomy between unbridged and bridged zirconocene derivatives with regard to tetranuclear versus binuclear product formation is proposed to be connected to different degrees of rotational freedom of their C5-ring ligands. Alkylaluminum-complexed zirconocene dihydrides, previously observed in zirconocene-based precatalyst systems activated by methylalumoxane (MAO) upon addition of HAI'Bu2 or Al iBu3, are proposed to be species of the type Me2Si(ind)2Zr(Me)(μ-H) 2Al iBu2, stabilized by interaction of their terminal Me group with a Lewis acidic site of MAO.