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

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

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BALDWIN, Steven M., John E. BERCAW, Lawrence M. HENLING, Michael W. DAY, Hans-Herbert BRINTZINGER, 2011. Cationic alkylaluminum-complexed zirconocene hydrides : NMR-spectroscopic identification, crystallographic structure determination, and interconversion with other zirconocene cations. In: Journal of the American Chemical Society. 133(6), pp. 1805-1813. ISSN 0002-7863. eISSN 1520-5126

@article{Baldwin2011-02-16Catio-23661, title={Cationic alkylaluminum-complexed zirconocene hydrides : NMR-spectroscopic identification, crystallographic structure determination, and interconversion with other zirconocene cations}, year={2011}, doi={10.1021/ja1050428}, number={6}, volume={133}, issn={0002-7863}, journal={Journal of the American Chemical Society}, pages={1805--1813}, author={Baldwin, Steven M. and Bercaw, John E. and Henling, Lawrence M. and Day, Michael W. and Brintzinger, Hans-Herbert} }

Day, Michael W. Bercaw, John E. Brintzinger, Hans-Herbert Brintzinger, Hans-Herbert 2013-06-17T13:39:13Z Day, Michael W. Bercaw, John E. Henling, Lawrence M. 2011-02-16 The ansa-zirconocene complex rac-Me<sub>2</sub>Si(1-indenyl)<sub>2</sub>ZrCl<sub>2</sub> ((SBI)ZrCl<sub>2</sub>) reacts with diisobutylaluminum hydride and trityl tetrakis(perfluorophenyl)borate in hydrocarbon solutions to give the cation [(SBI)Zr(μ-H)<sub>3</sub>(AliBu<sub>2</sub>)<sub>2</sub>]<sup>+</sup>, 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)<sup>3</sup>(AliBu<sub>2</sub>)<sub>2</sub>]<sup>+</sup> reacts reversibly with ClAliBu<sub>2</sub> to give the dichloro-bridged cation [(SBI)Zr(μ-Cl)<sub>2</sub>AliBu<sub>2</sub>]<sup>+</sup>. Reaction with AlMe<sub>3</sub> first leads to mixed-alkyl species [(SBI)Zr(μ-H)<sub>3</sub>(AlMexiBu<sub>2</sub>−x)<sub>2</sub>]<sup>+</sup> by exchange of alkyl groups between aluminum centers. At higher AlMe<sub>3</sub>/Zr ratios, [(SBI)Zr(μ-Me)<sub>2</sub>AlMe<sub>2</sub>]<sup>+</sup>, a constituent of methylalumoxane-activated catalyst systems, is formed in an equilibrium, in which the hydride cation [(SBI)Zr(μ-H)<sub>3</sub>(AlR<sub>2</sub>)<sub>2</sub>]<sup>+</sup> strongly predominates at comparable HAliBu<sub>2</sub> and AlMe<sub>3</sub> concentrations, thus implicating the presence of this hydride cation in olefin polymerization catalyst systems. Henling, Lawrence M. eng Cationic alkylaluminum-complexed zirconocene hydrides : NMR-spectroscopic identification, crystallographic structure determination, and interconversion with other zirconocene cations Baldwin, Steven M. 2013-06-17T13:39:13Z Journal of American Chemical Society ; 133 (2011), 6. - S. 1805-1813 deposit-license Baldwin, Steven M.

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