Stepwise Functionalization of N<sub>2</sub> at Mo: Nitrido to Imido to Amido – Factors Favoring Amine Elimination from the Amido Complex
Soukaina Bennaamane, Marı́a F. Espada, Ikram Yagoub, Nathalie Saffon‐Merceron, Noel Nebra, Marie Fustier‐Boutignon, Eric Clot, Nicolas Mézailles
Abstract
Functionalization of nitrido complex [(P Ph P 2 Cy )Mo(N)( I )] by a bis‐silane in concentrated medium generates the hydrido‐imido complex [(P Ph P 2 Cy )Mo(H)(=NSiMe 2 CH 2 CH 2 SiMe 2 H)(I)]. Abstraction of the iodide by thallium salt TlX (X = PF 6 , OTf) results in a second N–Si bond formation and forms the bis‐hydride amide complex [(P Ph P 2 Cy )Mo(H) 2 (NSiMe 2 CH 2 CH 2 SiMe 2 )] + . An alternative synthesis relies on the abstraction of the iodide from the nitride complex [(P Ph P 2 Cy )Mo(N)(I)] to generate the corresponding cationic complex [(P Ph P 2 Cy )Mo(N)] + followed by addition of the bis‐silane. Addition of PMe 3 to the [(P Ph P 2 Cy )Mo(H) 2 (NSiMe 2 CH 2 CH 2 SiMe 2 )] + complex liberates the silylamine and forms the Mo (II) cationic complex [(P Ph P 2 Cy )Mo(H)(PMe 3 )] + . DFT calculations rationalizing the observed reactivity are presented.