Stepwise Functionalization of N 2 at Mo: Nitrido to Imido to Amido - Factors Favoring Amine Elimination from the Amido Complex

Soukaina Bennaamane (1) , Maria F Espada (1) , Ikram Yagoub , Nathalie Saffon‐merceron (2) , Noel Nebra (1) , Marie Fustier-Boutignon (1) , Eric Clot (3) , Nicolas Mézailles (1)

1 LHFA - Laboratoire Hétérochimie Fondamentale et Appliquée
2 ICT - Institut de Chimie de Toulouse
3 ICGM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier

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.

Domaines: Chimie; Chimie de coordination; Catalyse; Chimie théorique et/ou physique

Soukaina Bennaamane, Maria F Espada, Ikram Yagoub, Nathalie Saffon‐merceron, Noel Nebra, et al.. Stepwise Functionalization of N 2 at Mo: Nitrido to Imido to Amido - Factors Favoring Amine Elimination from the Amido Complex. European Journal of Inorganic Chemistry, 2020, 2020 (15-16), pp.1499-1505. ⟨10.1002/ejic.201901295⟩. ⟨hal-03012876⟩