Publications [#231792] of Steven W. Baldwin

Journal Articles

1. Baldwin, SM; Bereaw, JE; Brintzinger, HH, Alkylaluminum-complexed zirconocene hydrides: Identification of hydride-bridged species by NMR spectroscopy, Journal of the American Chemical Society, vol. 130 no. 51 (December, 2008), pp. 17423-17433, American Chemical Society (ACS), ISSN 0002-7863 [doi]
   (last updated on 2026/01/22)

   Abstract:
   Reactions of unbridged zirconocene dichlorides, (R nC 5H 5-n) 2ZrCl 2 (n=0, 1, or 2), with diisobutylaluminum hydride (HAI'Bu 2) result in the formation of tetranuclear trihydride clusters of the type (R nC 5H 5-n) 2Zr(μ-H) 3(Al ⁱBu2)3(μ-CI) 2, which contain three [Al ⁱBu 2] units. Ring-bridged ansa-zirconocene dichlorides, Me2E(R nC 5H 4-n) 2ZrCl 2 with E=C or Si, on the other hand, are found to form binuclear dihydride complexes of the type Me2E(R nC 5H 4-n) 2Zr(CI)(μ-H) 2Al ⁱBu 2 with only one [AIBu 2] 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 C 5-ring ligands. Alkylaluminum-complexed zirconocene dihydrides, previously observed in zirconocene-based precatalyst systems activated by methylalumoxane (MAO) upon addition of HAI'Bu 2 or Al ⁱBu 3, are proposed to be species of the type Me 2Si(ind) 2Zr(Me)(μ-H) 2Al ⁱBu 2, stabilized by interaction of their terminal Me group with a Lewis acidic site of MAO. © 2008 American Chemical Society.