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 the mixture (PNPN)NbCl2(N[tBu]Ar) (2) and (PNP)Nb≡N(N[tBu]Ar) (3), both of which have been spectroscopically and crystallographically characterized, including 15N isotopic labelling studies. Complex 3 represents the first structural 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 then 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. This is in contrast to that of the reaction of 1 with NaOCP, where the (PNPP)NbCl(N[tBu][Ar]) complex was able to be isolated.

Isolation and characterization of a neutral and terminal niobium nitride

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