Ligand-Based Reduction of CO2 to CO Mediated by an Anionic Niobium Nitride Complex
The terminal nitride anion complex [Na][N≡Nb(N[tBu]Ar)3] ([Na][1], Ar = 3,5-Me2C6H3) reacts quantitatively with CO2 to give the carbamate complex [Na][O2CN≡Nb(N[tBu]Ar)3] ([Na][O2C-1]). The structure of [Na][O2C-1] as the bis-12-crown-4 solvate, as determined by X-ray crystallography, displays a uni...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society
2011
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| Online Access: | http://hdl.handle.net/1721.1/65162 https://orcid.org/0000-0003-2568-3269 |
| _version_ | 1826194808138366976 |
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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 | The terminal nitride anion complex [Na][N≡Nb(N[tBu]Ar)3] ([Na][1], Ar = 3,5-Me2C6H3) reacts quantitatively with CO2 to give the carbamate complex [Na][O2CN≡Nb(N[tBu]Ar)3] ([Na][O2C-1]). The structure of [Na][O2C-1] as the bis-12-crown-4 solvate, as determined by X-ray crystallography, displays a unique N-bound carbamate ligand without any metal−oxygen interactions. When treated with organic acid anhydrides or acid chlorides, complex [Na][O2C-1] reacts via salt elimination to give the five-coordinate complexes (RC(O)O)(OCN)Nb(N[tBu]Ar)3 (R-2, R = Me, tBu, F3C). We show that complexes R-2 yield the starting complex [Na][1] with concomitant release of CO upon two-electron reduction. This series of reactions constitutes a closed cycle for the conversion of CO2 to CO mediated by a terminal nitride anion complex. |
| first_indexed | 2024-09-23T10:02:29Z |
| format | Article |
| id | mit-1721.1/65162 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T10:02:29Z |
| publishDate | 2011 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | mit-1721.1/651622022-09-30T18:28:02Z Ligand-Based Reduction of CO2 to CO Mediated by an Anionic Niobium Nitride Complex Silvia, Jared Scott Cummins, Christopher C. Massachusetts Institute of Technology. Department of Chemistry Cummins, Christopher C. Silvia, Jared Scott Cummins, Christopher C. The terminal nitride anion complex [Na][N≡Nb(N[tBu]Ar)3] ([Na][1], Ar = 3,5-Me2C6H3) reacts quantitatively with CO2 to give the carbamate complex [Na][O2CN≡Nb(N[tBu]Ar)3] ([Na][O2C-1]). The structure of [Na][O2C-1] as the bis-12-crown-4 solvate, as determined by X-ray crystallography, displays a unique N-bound carbamate ligand without any metal−oxygen interactions. When treated with organic acid anhydrides or acid chlorides, complex [Na][O2C-1] reacts via salt elimination to give the five-coordinate complexes (RC(O)O)(OCN)Nb(N[tBu]Ar)3 (R-2, R = Me, tBu, F3C). We show that complexes R-2 yield the starting complex [Na][1] with concomitant release of CO upon two-electron reduction. This series of reactions constitutes a closed cycle for the conversion of CO2 to CO mediated by a terminal nitride anion complex. National Science Foundation (U.S.) (grant CHE-0802907) British Petroleum Company 2011-08-16T13:24:33Z 2011-08-16T13:24:33Z 2010-02 Article http://purl.org/eprint/type/JournalArticle 1520-5126 0002-7863 http://hdl.handle.net/1721.1/65162 Silvia, Jared S., and Christopher C. Cummins. “Ligand-Based Reduction of CO2 to CO Mediated by an Anionic Niobium Nitride Complex.” Journal of the American Chemical Society 132.7 (2010) : 2169-2171. https://orcid.org/0000-0003-2568-3269 en_US http://dx.doi.org/10.1021/ja910445r 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. Cummins |
| spellingShingle | Silvia, Jared Scott Cummins, Christopher C. Ligand-Based Reduction of CO2 to CO Mediated by an Anionic Niobium Nitride Complex |
| title | Ligand-Based Reduction of CO2 to CO Mediated by an Anionic Niobium Nitride Complex |
| title_full | Ligand-Based Reduction of CO2 to CO Mediated by an Anionic Niobium Nitride Complex |
| title_fullStr | Ligand-Based Reduction of CO2 to CO Mediated by an Anionic Niobium Nitride Complex |
| title_full_unstemmed | Ligand-Based Reduction of CO2 to CO Mediated by an Anionic Niobium Nitride Complex |
| title_short | Ligand-Based Reduction of CO2 to CO Mediated by an Anionic Niobium Nitride Complex |
| title_sort | ligand based reduction of co2 to co mediated by an anionic niobium nitride complex |
| url | http://hdl.handle.net/1721.1/65162 https://orcid.org/0000-0003-2568-3269 |
| work_keys_str_mv | AT silviajaredscott ligandbasedreductionofco2tocomediatedbyananionicniobiumnitridecomplex AT cumminschristopherc ligandbasedreductionofco2tocomediatedbyananionicniobiumnitridecomplex |