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Siloxyaluminum alkyl cations : syntheses, structures, and reactions related to activation of zirconocene catalysts on silica gel surfaces

Siloxyaluminum alkyl cations : syntheses, structures, and reactions related to activation of zirconocene catalysts on silica gel surfaces

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WROBEL, Olaf, Frank SCHAPER, Ulrich WIESER, Heike GREGORIUS, Hans-Herbert BRINTZINGER, 2003. Siloxyaluminum alkyl cations : syntheses, structures, and reactions related to activation of zirconocene catalysts on silica gel surfaces. In: Organometallics. 22(6), pp. 1320-1325. ISSN 0276-7333. eISSN 1520-6041

@article{Wrobel2003Silox-23727, title={Siloxyaluminum alkyl cations : syntheses, structures, and reactions related to activation of zirconocene catalysts on silica gel surfaces}, year={2003}, doi={10.1021/om0207515}, number={6}, volume={22}, issn={0276-7333}, journal={Organometallics}, pages={1320--1325}, author={Wrobel, Olaf and Schaper, Frank and Wieser, Ulrich and Gregorius, Heike and Brintzinger, Hans-Herbert} }

Gregorius, Heike Schaper, Frank 2003 Gregorius, Heike Brintzinger, Hans-Herbert Siloxyaluminum alkyl cations : syntheses, structures, and reactions related to activation of zirconocene catalysts on silica gel surfaces Wieser, Ulrich Binuclear siloxyaluminum methyl complexes of the type Me<sub>2</sub>Al(μ-OSiR<sub>3</sub>)<sub>2</sub>AlMe<sub>2</sub> react with protonated N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, with release of CH<sub>4</sub>, to form the dimethylaniline (DMA)-stabilized siloxyaluminum methyl cations Me<sub>2</sub>Al(μ-OSiR<sub>3</sub>)<sub>2</sub>AlMe(NMe<sub>2</sub>(C<sub>6</sub>H<sub>5</sub>)<sup>+</sup>. These cations abstract a Cl<sup>-</sup> ligand from (C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>ZrCl<sub>2</sub>, to give the dinuclear cation {(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>ZrCl}<sub>2</sub>(μ-Cl)<sup>+</sup>, and a CH<sub>3</sub><sup>-</sup> ligand from (C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>Zr(CH<sub>3</sub>)<sub>2</sub>, to give by way of the DMA-stabilized cation (C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>Zr(CH<sub>3</sub>)NMe<sub>2</sub>(C<sub>6</sub>H<sub>5</sub>)<sup>+</sup> the CH-activation product (C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>ZrCH<sub>2</sub>NMe(C<sub>6</sub>H<sub>5</sub>)<sup>+</sup>; reaction with Me<sub>2</sub>Si(ind)<sub>2</sub>ZrMe<sub>2</sub> in toluene solution yields a moderately active catalyst for ethene polymerization. This reactivity of siloxyaluminum methyl cations is qualitatively similar to, although substantially lower than, that of a silica gel surface treated with trimethylaluminum and a cationizing agent. 2013-06-20T15:08:49Z Brintzinger, Hans-Herbert Wieser, Ulrich deposit-license 2013-06-20T15:08:49Z eng Schaper, Frank Wrobel, Olaf Organometallics ; 22 (2003), 6. - S. 1320-1325 Wrobel, Olaf

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