Two-Electron Reduction of a Vanadium(V) Nitride by CO to Release Cyanate and Open a Coordination Site
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...
| Main Authors: | , |
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| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
American Chemical Society
2011
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| Online Access: | http://hdl.handle.net/1721.1/64710 https://orcid.org/0000-0003-2568-3269 |
| _version_ | 1811078581427634176 |
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| author | Silvia, Jared Scott Cummins, Christopher C. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Silvia, Jared Scott Cummins, Christopher C. |
| author_sort | Silvia, Jared Scott |
| collection | MIT |
| description | 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). |
| first_indexed | 2024-09-23T11:02:32Z |
| format | Article |
| id | mit-1721.1/64710 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T11:02:32Z |
| publishDate | 2011 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | mit-1721.1/647102022-09-27T16:41:35Z Two-Electron Reduction of a Vanadium(V) Nitride by CO to Release Cyanate and Open a Coordination Site Silvia, Jared Scott Cummins, Christopher C. Massachusetts Institute of Technology. Department of Chemistry Cummins, Christopher C. Cummins, Christopher C. Silvia, Jared Scott 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). BP (Firm) 2011-06-29T19:35:01Z 2011-06-29T19:35:01Z 2008-12 2008-10 Article http://purl.org/eprint/type/JournalArticle 1520-5126 0002-7863 http://hdl.handle.net/1721.1/64710 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. https://orcid.org/0000-0003-2568-3269 en_US http://dx.doi.org/10.1021/ja807767w Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society Prof. Christopher Cummins |
| spellingShingle | Silvia, Jared Scott Cummins, Christopher C. Two-Electron Reduction of a Vanadium(V) Nitride by CO to Release Cyanate and Open a Coordination Site |
| title | Two-Electron Reduction of a Vanadium(V) Nitride by CO to Release Cyanate and Open a Coordination Site |
| title_full | Two-Electron Reduction of a Vanadium(V) Nitride by CO to Release Cyanate and Open a Coordination Site |
| title_fullStr | Two-Electron Reduction of a Vanadium(V) Nitride by CO to Release Cyanate and Open a Coordination Site |
| title_full_unstemmed | Two-Electron Reduction of a Vanadium(V) Nitride by CO to Release Cyanate and Open a Coordination Site |
| title_short | Two-Electron Reduction of a Vanadium(V) Nitride by CO to Release Cyanate and Open a Coordination Site |
| title_sort | two electron reduction of a vanadium v nitride by co to release cyanate and open a coordination site |
| url | http://hdl.handle.net/1721.1/64710 https://orcid.org/0000-0003-2568-3269 |
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