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

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 an...

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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:
Catalysis
Chemical Sciences
Coordination chemistry
or physical chemistry
Theoretical and
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Summary: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.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.201901295