Issue 84, 2022

Ligand non-innocence allows isolation of a neutral and terminal niobium nitride

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)Nb[triple bond, length as m-dash]N(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.

Graphical abstract: Ligand non-innocence allows isolation of a neutral and terminal niobium nitride

Supplementary files

Article information

Article type
Communication
Submitted
24 Aug 2022
Accepted
19 Sep 2022
First published
20 Sep 2022

Chem. Commun., 2022,58, 11795-11798

Ligand non-innocence allows isolation of a neutral and terminal niobium nitride

S. Senthil, S. Kwon, H. Im, M. R. Gau, M. Baik and D. J. Mindiola, Chem. Commun., 2022, 58, 11795 DOI: 10.1039/D2CC04696B

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