Ligand non-innocence allows isolation of a neutral and terminal niobium nitride.
Chem Commun (Camb)
; 58(84): 11795-11798, 2022 Oct 20.
Article
em En
| MEDLINE
| ID: mdl-36193836
ABSTRACT
Complex (PNP)NbCl2(N[tBu]Ar) (1) (PNP- = N[2-PiPr2-4-methylphenyl]2; Ar = 3,5-Me2C6H3) reacts with one equiv. of NaN3 to form a mixture of (PNPN)NbCl2(N[tBu]Ar) (2) and (PNP)NbîN(N[tBu]Ar) (3), both of which have been spectroscopically and crystallographically characterized, including 15N isotopic labelling studies. Complex 3 represents the first structurally characterized example of a neutral and mononuclear Nb nitride. Independent studies established 3 to form via two-electron reduction of 2, whereas oxidation of 3 by two-electrons reversed the process. Computational studies suggest the transmetallation step to produce the intermediate [(PNP)NbCl(N3)(N[tBu]Ar)] (A) which extrudes N2 to form the phosphinimide [(PNPN)NbCl(N[tBu]Ar)] (B) followed by disproportionation to 2 and low-valent [(PNPN)Nb(N[tBu]Ar)] (C). The latter then undergoes intramolecular N-atom transfer to form the nitride moiety in 3.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Nióbio
Idioma:
En
Revista:
Chem Commun (Camb)
Assunto da revista:
QUIMICA
Ano de publicação:
2022
Tipo de documento:
Article
País de afiliação:
Estados Unidos