title: 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.
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(2C5H4N)(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.
authors.affiliation: Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, UK OX1 3QR.
authors.forename: Benjamin D
authors.initials: BD
authors.lastname: Ward
authors.forename: Eric
authors.initials: E
authors.lastname: Clot
authors.forename: Stuart R
authors.initials: SR
authors.lastname: Dubberley
authors.forename: Lutz H
authors.initials: LH
authors.lastname: Gade
authors.forename: Philip
authors.initials: P
authors.lastname: Mountford