Radical anionic versus neutral 2,2′-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands
The synthesis and characterization of (bipy)₂U(N[t-Bu]Ar)₂ (1-(bipy)₂, bipy = 2,2′-bipyridyl, Ar = 3,5-C₆H₃Me₂), (bipy)U(N[1Ad]Ar)₃ (2-bipy), (bipy)₂U(NC[t-Bu]Mes)₃ (3-(bipy)2, Mes = 2,4,6-C₆H₂Me₃), and IU(bipy)(NC[t-Bu]Mes)₃ (3-I-bipy) are reported. X-ray crystallography studies indicate that bipy...
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| Format: | Article |
| Language: | en_US |
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Royal Society of Chemistry
2018
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| Online Access: | http://hdl.handle.net/1721.1/115125 https://orcid.org/0000-0003-2568-3269 |
| _version_ | 1826194976859488256 |
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| author | Diaconescu, Paula L Cummins, Christopher C |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Diaconescu, Paula L Cummins, Christopher C |
| author_sort | Diaconescu, Paula L |
| collection | MIT |
| description | The synthesis and characterization of (bipy)₂U(N[t-Bu]Ar)₂ (1-(bipy)₂, bipy = 2,2′-bipyridyl, Ar = 3,5-C₆H₃Me₂), (bipy)U(N[1Ad]Ar)₃ (2-bipy), (bipy)₂U(NC[t-Bu]Mes)₃ (3-(bipy)2, Mes = 2,4,6-C₆H₂Me₃), and IU(bipy)(NC[t-Bu]Mes)₃ (3-I-bipy) are reported. X-ray crystallography studies indicate that bipy coordinates as a radical anion in 1-(bipy)₂ and 2-bipy, and as a neutral ligand in 3-I-bipy. In 3-(bipy)₂, one of the bipy ligands is best viewed as a radical anion, the other as a neutral ligand. The electronic structure assignments are supported by NMR spectroscopy studies of exchange experiments with 4,4′-dimethyl-2,2′-bipyridyl and also by optical spectroscopy. In all complexes, uranium was assigned a +4 formal oxidation state. |
| first_indexed | 2024-09-23T10:05:09Z |
| format | Article |
| id | mit-1721.1/115125 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T10:05:09Z |
| publishDate | 2018 |
| publisher | Royal Society of Chemistry |
| record_format | dspace |
| spelling | mit-1721.1/1151252022-09-30T18:50:02Z Radical anionic versus neutral 2,2′-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands Diaconescu, Paula L Cummins, Christopher C Massachusetts Institute of Technology. Department of Chemistry Cummins, Christopher C. Diaconescu, Paula L Cummins, Christopher C The synthesis and characterization of (bipy)₂U(N[t-Bu]Ar)₂ (1-(bipy)₂, bipy = 2,2′-bipyridyl, Ar = 3,5-C₆H₃Me₂), (bipy)U(N[1Ad]Ar)₃ (2-bipy), (bipy)₂U(NC[t-Bu]Mes)₃ (3-(bipy)2, Mes = 2,4,6-C₆H₂Me₃), and IU(bipy)(NC[t-Bu]Mes)₃ (3-I-bipy) are reported. X-ray crystallography studies indicate that bipy coordinates as a radical anion in 1-(bipy)₂ and 2-bipy, and as a neutral ligand in 3-I-bipy. In 3-(bipy)₂, one of the bipy ligands is best viewed as a radical anion, the other as a neutral ligand. The electronic structure assignments are supported by NMR spectroscopy studies of exchange experiments with 4,4′-dimethyl-2,2′-bipyridyl and also by optical spectroscopy. In all complexes, uranium was assigned a +4 formal oxidation state. National Science Foundation (U.S.) (Grant CHE-9988806) 2018-05-01T14:47:11Z 2018-05-01T14:47:11Z 2014-12 2014-08 Article http://purl.org/eprint/type/JournalArticle 1477-9226 1477-9234 http://hdl.handle.net/1721.1/115125 Diaconescu, Paula L. and Christopher C. Cummins. “Radical Anionic Versus Neutral 2,2′-Bipyridyl Coordination in Uranium Complexes Supported by Amide and Ketimide Ligands.” Dalton Transactions 44, 6 (2015): 2676–2683 © 2015 Royal Society of Chemistry https://orcid.org/0000-0003-2568-3269 en_US http://dx.doi.org/10.1039/C4DT02422B Dalton Transactions Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf Royal Society of Chemistry Prof. Cummins via Erja Kajosalo |
| spellingShingle | Diaconescu, Paula L Cummins, Christopher C Radical anionic versus neutral 2,2′-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands |
| title | Radical anionic versus neutral 2,2′-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands |
| title_full | Radical anionic versus neutral 2,2′-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands |
| title_fullStr | Radical anionic versus neutral 2,2′-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands |
| title_full_unstemmed | Radical anionic versus neutral 2,2′-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands |
| title_short | Radical anionic versus neutral 2,2′-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands |
| title_sort | radical anionic versus neutral 2 2 bipyridyl coordination in uranium complexes supported by amide and ketimide ligands |
| url | http://hdl.handle.net/1721.1/115125 https://orcid.org/0000-0003-2568-3269 |
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