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Synthesis and reactivity of the imidotungsten methyl cation [W(N(2)Npy)(NPh)Me](+): CO2 adds to the W=NPh bond and does not insert into the W-Me bond

Ward, Benjamin David, Clot, E., Dubberley, S. R., Gade, L. H. and Mountford, P. 2002. Synthesis and reactivity of the imidotungsten methyl cation [W(N(2)Npy)(NPh)Me](+): CO2 adds to the W=NPh bond and does not insert into the W-Me bond. Chemical Communications (22) , pp. 2618-2619. 10.1039/B208327B

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Abstract

The imidotungsten dimethyl compound [W(N2Npy)(NPh)Me2] 2 reacts with BArF3 to form the cationic complex [W(N2Npy)(NPh)Me]+ 3+ [anion = [MeBArF3]−; ArF = C6F5; N2Npy = MeC(2-C5H4N)(CH2NSiMe3)2] which undergoes methyl group exchange with added 2, [Cp2ZrMe2] or ZnMe2; treatment of cation 3+ with CO2 or isocyanates leads to cycloaddition reactions at the WNPh bond and not insertion into the W–Me bond, despite the latter product being the most thermodynamically favourable according to DFT calculations.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: RSC Publishing
ISSN: 1359-7345
Last Modified: 04 Jun 2017 02:08
URI: http://orca.cf.ac.uk/id/eprint/9708

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