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

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.
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https://hal.archives-ouvertes.fr/hal-03012876
Contributor : Nicolas Mézailles Connect in order to contact the contributor
Submitted on : Wednesday, October 27, 2021 - 2:22:31 PM
Last modification on : Wednesday, November 3, 2021 - 3:59:37 AM

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Soukaina Bennaamane, Maria 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, Wiley-VCH Verlag, 2020, 2020 (15-16), pp.1499-1505. ⟨10.1002/ejic.201901295⟩. ⟨hal-03012876⟩

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