Synthesis and reactivity of the imidotungsten methyl cation [W(N<sub>2</sub>Npy)(NPh)Me]<sup>+</sup>: CO<sub>2</sub> adds to the W=NPh bond and does not insert into the W-Me bond - CNRS - Centre national de la recherche scientifique Accéder directement au contenu
Article Dans Une Revue Chemical Communications Année : 2002

Synthesis and reactivity of the imidotungsten methyl cation [W(N2Npy)(NPh)Me]+: CO2 adds to the W=NPh bond and does not insert into the W-Me bond

Résumé

The imidotungsten dimethyl compound [W(N2Npy)(NPh)Me-2] 2 reacts with BAr3F to form the cationic complex [W(N2Npy)(NPh)Me](+) 3(+) [anion = [Me-BAr3F]-; Ar-F 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 W=NPh bond and not insertion into the W-Me bond, despite the latter product being the most thermodynamically favourable according to DFT calculations.

Dates et versions

hal-00429097 , version 1 (30-10-2009)

Identifiants

Citer

Benjamin D. Ward, Eric Clot, Stuart R. Dubberley, Lutz H. Gade, Philip Mountford. Synthesis and reactivity of the imidotungsten methyl cation [W(N2Npy)(NPh)Me]+: CO2 adds to the W=NPh bond and does not insert into the W-Me bond. Chemical Communications, 2002, pp.2618-2619. ⟨10.1039/b208327b⟩. ⟨hal-00429097⟩
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