Two-Electron Reduction of a Vanadium(V) Nitride by CO to Release Cyanate and Open a Coordination Site
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Author(s)
Silvia, Jared Scott
Cummins, Christopher C.
Date Issued
December 2008
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society
Citation
Silvia, Jared S., and Christopher C. Cummins. “Two-Electron Reduction of a Vanadium(V) Nitride by CO To Release Cyanate and Open a Coordination Site.” Journal of the American Chemical Society 131.2 (2009) : 446-447.
Version
Author's final manuscript
Abstract
Generation of the nitrido functional group is commonly
achieved by treatment of metal complexes with azide sources
and is fostered by N2 extrusion.1 The analogous transformation
involving isocyanate and production of CO is less well
documented. A previous study by Fickes et al. showed that the
1e reduction of a niobium(IV) isocyanate complex
(OCN)Nb(N[t-Bu]Ar)3 (1-Nb(NCO), Ar = 3,5-Me2C6H3)
results in formation of a nucleophilic, anionic terminal nitride
complex [NNb(N[t-Bu]Ar)3]– (1-NbN–) with concomitant
evolution of CO.2 This, to the best of our knowledge, is the
only example of terminal metal nitride derivation from an
isocyanate ligand (Scheme 1A).2,3 Curious as to the generality
of this reductive decarbonylation, we sought to synthesize the
analogous vanadium isocyanate complex (OCN)V(N[t-
Bu]Ar)3 (1-V(NCO)) to compare its reactivity with that of 1-
Nb(NCO).
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/ja807767w
