Atom- and Group Transfers to MIV Oxo and Imido Complexes, (η5-C5Me5)M[N(iPr)C(Me)N(iPr)](E) (M = Mo, W; E = O, NSiMe3): Orthogonal Generation of a MVI Terminal Nitride via Inter-ligand Silyl Group Migration

The group 6 MIV terminal oxo complexes, Cp*M[N(iPr)C(Me)N(iPr)](O) (Cp* = η5‐C5Me5) where M = Mo (1) and W (2) react with N3SiMe3 to provide the MVI terminal nitrido complexes, Cp*M[N(iPr)C(Me)N(iPr)](N)(OSiMe3) where M = Mo (5) and W (7), respectively. A mechanism involving nitrene group transfer to generate a MVI oxo, imido intermediate, followed by inter‐ligand silyl group transfer is proposed to account for formation of 5 and 7. Compound 7 was alternatively prepared through an orthogonal route to the same proposed intermediate involving oxygen atom transfer from N2O to the WIV terminal imido complex Cp*W[N(iPr)C(Me)N(iPr)](NSiMe3) (4). The nucleophilicity of the terminal nitride 7 was further established through methylation to provide cationic {Cp*W[N(iPr)C(Me)N(iPr)](NMe)(OSiMe3)}{I} (8).