| Spin-State Dependent Radical Stabilization in Nitrenes: The Unusually Small Singlet-Triplet Splitting in 2-Furanylnitrene. | |
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MedLine Citation:
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PMID: 22059601 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
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Geometries and energies of the triplet and singlet states of 2-furanylnitrene and 3-furanylnitrene have been calculated by using spin-flip coupled-cluster methods. Calculations with triple-zeta basis sets predict a singlet-triplet splitting of 10.9 kcal/mol for 2-furanylnitrene, 4.5 kcal/mol smaller than that in phenylnitrene. In contrast, the singlet-triplet splitting in 3-furanylnitrene is computed to be 1.9 kcal/mol larger than that in phenylnitrene. The differences in the singlet-triplet splittings for the furanylnitrenes are attributed to the differences in the radical stabilizing abilities of the 2-furanyl- and 3-furanyl-groups compared to a phenyl ring. Comparison of the singlet-triplet splittings of more than 20 substituted aromatic nitrenes and the radical stabilizing ability of the aromatic systems reveals a high degree of correlation between the singlet-triplet splitting and the radical stabilizing ability, indicating that singlet states of aromatic nitrenes are preferentially stabilized by radical stabilizing substituents. The preferential stabilization of the singlet states is attributed to the decrease in electron pair repulsion resulting from increased delocalization of the radical electron. |
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Authors:
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Paul G Wenthold |
Publication Detail:
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Type: JOURNAL ARTICLE Date: 2011-11-7 |
Journal Detail:
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Title: The Journal of organic chemistry Volume: - ISSN: 1520-6904 ISO Abbreviation: - Publication Date: 2011 Nov |
Date Detail:
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Created Date: 2011-11-8 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 2985193R Medline TA: J Org Chem Country: - |
Other Details:
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Languages: ENG Pagination: - Citation Subset: - |
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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