Irikura, Karl K. and Goddard, W. A., III and Beauchamp, J. L. (1992) Singlet-triplet gaps in substituted carbenes CXY (X, Y = H, F, Cl, Br, I, SiH_3). Journal of the American Chemical Society, 114 (1). pp. 48-51. ISSN 0002-7863. doi:10.1021/ja00027a006. https://resolver.caltech.edu/CaltechAUTHORS:20171122-111333892
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Abstract
Trends in the singlet-triplet state-splittings of substituted carbenes are found to be reproduced accurately with a very simple level of ab initio theory. The minimum balanced description, GVB(1/2), with a simple basis set yields singlet-triplet gaps that correlate linearly with available accurate values. This linear relationship is exploited to predict the state-splitting for the remaining members of the title series of carbenes. The magnitudes of the singlet-triplet splittings can be rationalized in terms of the charge on the carbenic carbon atom as well as π-donation from the substituents. The correlation with charge, in conjunction with electronegativity equalization, permits singlet-triplet gaps to be predicted for arbitrary simple carbenes using only a hand calculator. Since both charge and π-donation are important in determining the energy gaps, we conclude that σ-donation and π-backbonding act synergistically.
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| Alternate Title: | Singlet-triplet gaps in substituted carbenes CXY (X, Y = H, fluoro, chloro, bromo, iodo, silyl) | |||||||||
| Additional Information: | © 1992 American Chemical Society. Received July 1, 1991. We are grateful to the National Science Foundation for support under Grants CHE-83-18041 (W.A.G.) and CHE-87-11567 (J.L.B.). K.K.I. appreciates fellowship support from the Department of Education and thanks J. F. Liebman for helpful comments. | |||||||||
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| Issue or Number: | 1 | |||||||||
| DOI: | 10.1021/ja00027a006 | |||||||||
| Record Number: | CaltechAUTHORS:20171122-111333892 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20171122-111333892 | |||||||||
| Official Citation: | Singlet-triplet gaps in substituted carbenes CXY (X, Y = H, fluoro, chloro, bromo, iodo, silyl). Karl K. Irikura, W. A. Goddard III, and J. L. Beauchamp. Journal of the American Chemical Society 1992 114 (1), 48-51 DOI: 10.1021/ja00027a006 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 83433 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Tony Diaz | |||||||||
| Deposited On: | 22 Nov 2017 19:27 | |||||||||
| Last Modified: | 15 Nov 2021 19:58 |
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