rac-Me 2 Si(2-Me-4-t-Bu-C 5 H 2) 2 ZrMe + : an alkyl zirconocenium cation stabilized by steric shielding against interaction with ancillary ligands
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Organometallics. 2005, 24(5), pp. 867-871. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om049139z
Zusammenfassung
The sterically shielded cation rac-Me2Si(2-Me-4-t-Bu-C5H2)2ZrMe+, generated by reaction of rac-Me2Si(2-Me-4-t-Bu-C5H2)2ZrMe2 with methylalumoxane (MAO) or with dimethylanilinium or trityl perfluorotetraphenylborate, differs from other, more open zirconocene methyl cations in that it does not form the symmetric AlMe3 adduct rac-Me2Si(2-Me-4-t-Bu-C5H2)2Zr(μ-Me)2AlMe2+. Instead, the unsymmetric ternary adduct rac-Me2Si(2-Me-4-t-Bu-C5H2)2ZrMe(μ-Me)AlMe3−NMe2Ph+ is formed in the presence of dimethylaniline and trimethylaluminum. UV/vis and 1H NMR characteristics of hydrocarbon solutions containing rac-Me2Si(2-Me-4-t-Bu-C5H2)2ZrMe+***B(C6F5)4- or rac-Me2Si(2-Me-4-t-Bu-C5H2)2ZrMe+***MAOMe- indicate that cation−anion association in these ion pairs is unusually weak.
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SCHRÖDER, Lars, Hans-Herbert BRINTZINGER, Dmitrii E. BABUSHKIN, David FISCHER, Rolf MÜLHAUPT, 2005. rac-Me 2 Si(2-Me-4-t-Bu-C 5 H 2) 2 ZrMe + : an alkyl zirconocenium cation stabilized by steric shielding against interaction with ancillary ligands. In: Organometallics. 2005, 24(5), pp. 867-871. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om049139zBibTex
@article{Schroder2005racMe-23720,
year={2005},
doi={10.1021/om049139z},
title={rac-Me 2 Si(2-Me-4-t-Bu-C 5 H 2) 2 ZrMe + : an alkyl zirconocenium cation stabilized by steric shielding against interaction with ancillary ligands},
number={5},
volume={24},
issn={0276-7333},
journal={Organometallics},
pages={867--871},
author={Schröder, Lars and Brintzinger, Hans-Herbert and Babushkin, Dmitrii E. and Fischer, David and Mülhaupt, Rolf}
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<dcterms:abstract xml:lang="eng">The sterically shielded cation rac-Me<sub>2</sub>Si(2-Me-4-t-Bu-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>ZrMe<sup>+</sup>, generated by reaction of rac-Me<sub>2</sub>Si(2-Me-4-t-Bu-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>ZrMe<sub>2</sub> with methylalumoxane (MAO) or with dimethylanilinium or trityl perfluorotetraphenylborate, differs from other, more open zirconocene methyl cations in that it does not form the symmetric AlMe<sub>3</sub> adduct rac-Me<sub>2</sub>Si(2-Me-4-t-Bu-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>Zr(μ-Me)<sub>2</sub>AlMe<sub>2</sub><sup>+</sup>. Instead, the unsymmetric ternary adduct rac-Me<sub>2</sub>Si(2-Me-4-t-Bu-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>ZrMe(μ-Me)AlMe<sub>3</sub>−NMe<sub>2</sub>Ph<sup>+</sup> is formed in the presence of dimethylaniline and trimethylaluminum. UV/vis and <sup>1</sup>H NMR characteristics of hydrocarbon solutions containing rac-Me<sub>2</sub>Si(2-Me-4-t-Bu-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>ZrMe<sup>+</sup>***B(C<sub>6</sub>F<sub>5</sub>)4- or rac-Me<sub>2</sub>Si(2-Me-4-t-Bu-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>ZrMe<sup>+</sup>***MAOMe<sup>-</sup> indicate that cation−anion association in these ion pairs is unusually weak.</dcterms:abstract>
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