Cationic alkylaluminum-complexed zirconocene hydrides: NMR-spectroscopic identification, crystallographic structure determination, and interconversion with other zirconocene cations

Journal Article

The ansa-zirconocene complex rac-Me2Si(1-indenyl) 2ZrCl2 ((SBI)ZrCl2) reacts with diisobutylaluminum hydride and trityl tetrakis(perfluorophenyl)borate in hydrocarbon solutions to give the cation [(SBI)Zr(μ-H)3(Al iBu2)2]+, the identity of which is derived from NMR data and supported by a crystallographic structure determination. Analogous reactions proceed with many other zirconocene dichloride complexes. [(SBI)Zr(μ-H)3(AliBu 2)2]+ reacts reversibly with ClAl iBu2 to give the dichloro-bridged cation [(SBI)Zr(μ-Cl)2AliBu2]+. Reaction with AlMe3 first leads to mixed-alkyl species [(SBI)Zr(μ-H) 3(AlMexiBu2-x)2] + by exchange of alkyl groups between aluminum centers. At higher AlMe3/Zr ratios, [(SBI)Zr(μ-Me)2AlMe2] +, a constituent of methylalumoxane-activated catalyst systems, is formed in an equilibrium, in which the hydride cation [(SBI)Zr(μ-H) 3(AlR2)2]+ strongly predominates at comparable HAliBu2 and AlMe3 concentrations, thus implicating the presence of this hydride cation in olefin polymerization catalyst systems. © 2011 American Chemical Society.

Full Text

Duke Authors

Cited Authors

  • Baldwin, SM; Bercaw, JE; Henling, LM; Day, MW; Brintzinger, HH

Published Date

  • 2011

Published In

Volume / Issue

  • 133 / 6

Start / End Page

  • 1805 - 1813

International Standard Serial Number (ISSN)

  • 0002-7863

Digital Object Identifier (DOI)

  • 10.1021/ja1050428