Stepwise Functionalization of N2 at Mo: Nitrido to Imido to Amido – Factors Favoring Amine Elimination from the Amido Complex

Functionalization of nitrido complex [(PPhP2Cy)Mo(N)(I)] by a bis‐silane in concentrated medium generates the hydrido‐imido complex [(PPhP2Cy)Mo(H)(=NSiMe2CH2CH2SiMe2H)(I)]. ion of the iodide by thallium salt TlX (X = PF6, OTf) results in a second N–Si bond formation and forms the bis‐hydride amide...

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Bibliographic Details
Published in:European journal of inorganic chemistry 2020-04, Vol.2020 (15-16), p.1499-1505
Main Authors: Bennaamane, Soukaina, Espada, Maria F., Yagoub, Ikram, Saffon‐Merceron, Nathalie, Nebra, Noel, Fustier‐Boutignon, Marie, Clot, Eric, Mézailles, Nicolas
Format: Article
Language:English
Subjects:
Bis‐silane
Cations
Hydride ligands
Inorganic chemistry
Molybdenum
Nitride functionalization
Nitrogen reduction
Thallium
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Summary:Functionalization of nitrido complex [(PPhP2Cy)Mo(N)(I)] by a bis‐silane in concentrated medium generates the hydrido‐imido complex [(PPhP2Cy)Mo(H)(=NSiMe2CH2CH2SiMe2H)(I)]. ion 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 [(PPhP2Cy)Mo(H)2(NSiMe2CH2CH2SiMe2)]+. An alternative synthesis relies on the ion of the iodide from the nitride complex [(PPhP2Cy)Mo(N)(I)] to generate the corresponding cationic complex [(PPhP2Cy)Mo(N)]+ followed by addition of the bis‐silane. Addition of PMe3 to the [(PPhP2Cy)Mo(H)2(NSiMe2CH2CH2SiMe2)]+ complex liberates the silylamine and forms the Mo(II) cationic complex [(PPhP2Cy)Mo(H)(PMe3)]+. DFT calculations rationalizing the observed reactivity are presented. Nitride is functionalized by bis‐Si–H bonds to (bis‐silyl)amine, revealing a new route of stepwise functionalization of a nitride complex to silylamine under mild conditions.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.201901295