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ansa-titanocene catalysts for α-olefin polymerization : syntheses, structures, and reactions with methylaluminoxane and boron-based activators

ansa-titanocene catalysts for α-olefin polymerization : syntheses, structures, and reactions with methylaluminoxane and boron-based activators

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BRYLIAKOV, Konstantin P., Dmitrii E. BABUSHKIN, Evgenii P. TALSI, Alexander Z. VOSKOBOYNIKOV, Holger GRITZO, Lars SCHRÖDER, Hans-Robert H. DAMRAU, Ulrich WIESER, Frank SCHAPER, Hans-Herbert BRINTZINGER, 2005. ansa-titanocene catalysts for α-olefin polymerization : syntheses, structures, and reactions with methylaluminoxane and boron-based activators. In: Organometallics. 24(5), pp. 894-904. ISSN 0276-7333. eISSN 1520-6041

@article{Bryliakov2005ansa--23699, title={ansa-titanocene catalysts for α-olefin polymerization : syntheses, structures, and reactions with methylaluminoxane and boron-based activators}, year={2005}, doi={10.1021/om0492496}, number={5}, volume={24}, issn={0276-7333}, journal={Organometallics}, pages={894--904}, author={Bryliakov, Konstantin P. and Babushkin, Dmitrii E. and Talsi, Evgenii P. and Voskoboynikov, Alexander Z. and Gritzo, Holger and Schröder, Lars and Damrau, Hans-Robert H. and Wieser, Ulrich and Schaper, Frank and Brintzinger, Hans-Herbert} }

Babushkin, Dmitrii E. Schaper, Frank Talsi, Evgenii P. Talsi, Evgenii P. Brintzinger, Hans-Herbert Organometallics ; 24 (2005), 5. - S. 894-904 2013-06-20T14:54:28Z Voskoboynikov, Alexander Z. Brintzinger, Hans-Herbert Wieser, Ulrich Damrau, Hans-Robert H. eng Gritzo, Holger 2013-06-20T14:54:28Z Voskoboynikov, Alexander Z. 2005 ansa-titanocene catalysts for α-olefin polymerization : syntheses, structures, and reactions with methylaluminoxane and boron-based activators Schaper, Frank Gritzo, Holger deposit-license Wieser, Ulrich Schröder, Lars Schröder, Lars The racemic isomers of C<sub>2</sub>H<sub>4</sub>(1-Ind)<sub>2</sub>TiCl<sub>2</sub> and Me<sub>2</sub>Si(2-Me-Benzind)<sub>2</sub>TiMe<sub>2</sub> were synthesized and structurally characterized. Reactions of these and related ansa-titanocene complexes with methylaluminoxane or with the cationizing reagent [CPh<sub>3</sub>]<sup>+</sup>[B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>]<sup>-</sup>/Al<sub>2</sub>Me<sub>6</sub> were monitored by UV/vis, <sup>1</sup>H NMR, and EPR methods. Under conditions approaching those typically used in olefin polymerizations, heterobinuclear cations of the type [DianTiIV(μ-Me)<sub>2</sub>AlMe<sub>2</sub>]<sup>+</sup> (with Dian = bridged ligand dianion) dominate in each of these reaction systems, which catalyze the polymerization of propene at temperatures below ambient. Above 0 °C, these cations are reduced, mainly to neutral heterobinuclear species DianTiIII(μ-Me)<sub>2</sub>AlMe<sub>2</sub>, which appear to be inactive with regard to polymerization catalysis. In the absence of monomer, the main reducing agent appears to be ethyl aluminum admixtures in Al<sub>2</sub>Me<sub>6</sub>. Addition of monomer increases the rate of reduction rather drastically, probably via formation of titanium hydrides. Bryliakov, Konstantin P. Bryliakov, Konstantin P. Damrau, Hans-Robert H. Babushkin, Dmitrii E.

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