sigma*-aromaticity of substituted 1H-phosphirenium cations and substituted silacyclopropenes
Göller AH, Clark T (1996)
Publication Status: Published
Publication Type: Journal article
Publication year: 1996
Journal
Publisher: American Chemical Society
Book Volume: 61
Pages Range: 5840-5846
Journal Issue: 17
DOI: 10.1021/jo960387h
Abstract
The influence of the electronegativity of the ligands Y (F, Cl, Br, I, OH, NH2, CH3, H) on the strength of the sigma*-aromatic effect in gem-disubstituted 1H-Phosphirenium cations and substituted 3-silacyclopropenes has been investigated with ab initio theory. Phosphorus and silicon provide a low lying p-type sigma*-orbital antibonding to the ligands Y. This interacts with the ring double bond analogously to a third p-orbital in a 2 pi Huckel system. These systems have bean compared to the analogous saturated rings. Calculations at the RHF/6-31G* and MP4/6-31+G* levels, NBO analyses of the effect of the ligands Y and comparisons of the relative stabilities of the saturated and unsaturated compounds suggest a weak but significant sigma*-aromatic effect dependent on the electronegativity of Y.
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Germany (DE)How to cite
APA:
Göller, A.H., & Clark, T. (1996). sigma*-aromaticity of substituted 1H-phosphirenium cations and substituted silacyclopropenes. Journal of Organic Chemistry, 61(17), 5840-5846. https://dx.doi.org/10.1021/jo960387h
MLA:
Göller, Andreas H., and Timothy Clark. "sigma*-aromaticity of substituted 1H-phosphirenium cations and substituted silacyclopropenes." Journal of Organic Chemistry 61.17 (1996): 5840-5846.
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