Publikation: Siloxyaluminum alkyl cations : syntheses, structures, and reactions related to activation of zirconocene catalysts on silica gel surfaces
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Binuclear siloxyaluminum methyl complexes of the type Me2Al(μ-OSiR3)2AlMe2 react with protonated N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, with release of CH4, to form the dimethylaniline (DMA)-stabilized siloxyaluminum methyl cations Me2Al(μ-OSiR3)2AlMe(NMe2(C6H5)+. These cations abstract a Cl- ligand from (C5H5)2ZrCl2, to give the dinuclear cation {(C5H5)2ZrCl}2(μ-Cl)+, and a CH3- ligand from (C5H5)2Zr(CH3)2, to give by way of the DMA-stabilized cation (C5H5)2Zr(CH3)NMe2(C6H5)+ the CH-activation product (C5H5)2ZrCH2NMe(C6H5)+; reaction with Me2Si(ind)2ZrMe2 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.
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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. 2003, 22(6), pp. 1320-1325. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om0207515BibTex
@article{Wrobel2003Silox-23727, year={2003}, doi={10.1021/om0207515}, title={Siloxyaluminum alkyl cations : syntheses, structures, and reactions related to activation of zirconocene catalysts on silica gel surfaces}, 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} }
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