Atom‐ and Group Transfers to M IV Oxo and Imido Complexes, (η 5 ‐C 5 Me 5 )M[N( i Pr)C(Me)N( i Pr)](E) (M = Mo, W; E = O, NSiMe 3 ): Orthogonal Generation of a M VI Terminal Nitride via Inter‐ligand Silyl Group Migration

The group 6 M IV terminal oxo complexes, Cp*M[N( i Pr)C(Me)N( i Pr)](O) (Cp* = η 5 ‐C 5 Me 5 ) where M = Mo ( 1 ) and W ( 2 ) react with N 3 SiMe 3 to provide the M VI terminal nitrido complexes, Cp*M[N( i Pr)C(Me)N( i Pr)](N)(OSiMe 3 ) where M = Mo ( 5 ) and W ( 7 ), respectively. A mechanism involving nitrene group transfer to generate a M VI 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 N 2 O to the W IV terminal imido complex Cp*W[N( i Pr)C(Me)N( i Pr)](NSiMe 3 ) ( 4 ). The nucleophilicity of the terminal nitride 7 was further established through methylation to provide cationic {Cp*W[N( i Pr)C(Me)N( i Pr)](NMe)(OSiMe 3 )}{I} ( 8 ).