Premium
Stepwise Functionalization of N 2 at Mo: Nitrido to Imido to Amido – Factors Favoring Amine Elimination from the Amido Complex
Author(s) -
Bennaamane Soukaina,
Espada Maria F.,
Yagoub Ikram,
SaffonMerceron Nathalie,
Nebra Noel,
FustierBoutig Marie,
Clot Eric,
Mézailles Nicolas
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201901295
Subject(s) - chemistry , silane , cationic polymerization , iodide , amide , amine gas treating , hydride , reactivity (psychology) , medicinal chemistry , methyl iodide , stereochemistry , polymer chemistry , organic chemistry , metal , medicine , alternative medicine , pathology
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.