Abstract
Functionalization of nitrido complex [(P Ph P2 Cy)Mo(N)(I)] by a bis-silane in concentrated medium generates the hydrido-imido complex [(P Ph P2 Cy)Mo(H)(=NSiMe2CH2CH2SiMe2H)(I)]. Abstraction of the iodide by thallium salt TlX (X = PF6, OTf) results in a second N─Si bond formation and forms the bis-hydride amide complex [(P Ph P2 Cy)Mo(H)2(NSiMe2CH2CH2SiMe2)] +. An alternative synthesis relies on the abstraction of the iodide from the nitride complex [(P Ph P2 Cy)Mo(N)(I)] to generate the corresponding cationic complex [(P Ph P2 Cy)Mo(N)] + followed by addition of the bis-silane. Addition of PMe3 to the [(P Ph P2 Cy)Mo(H)2(NSiMe2CH2CH2SiMe2)] + complex liberates the silylamine and forms the Mo (II) cationic complex [(P Ph P2 Cy)Mo(H)(PMe3)] +. DFT calculations rationalizing the observed reactivity are presented.