Ab initio study of the solvent effects on the singlet-triplet gap of nitrenium ions and carbenes

被引:58
作者
Gonzalez, C [1 ]
Restrepo-Cossio, A
Márquez, M
Wiberg, KB
De Rosa, M
机构
[1] Carnegie Mellon Univ, Pittsburgh Supercomp Ctr, Pittsburgh, PA 15213 USA
[2] Florida Atlantic Univ, Dept Chem, Boca Raton, FL 33431 USA
[3] Yale Univ, Dept Chem, New Haven, CT 06520 USA
[4] Penn State Univ, Dept Chem, Media, PA 19063 USA
关键词
D O I
10.1021/jp981150n
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Highly correlated ab initio molecular orbital methodologies have been used in the study of substituent effects on the singlet-triplet gaps of a series of nitrenium ions and their corresponding isoelectronic carbenes. Calculations in solution were carried out with the isodensity polarizable continuum models, IPCM. The results show a net stabilization of the singlet species as a result of electronic density donation of the substituents to a vacant p orbital located in the central atom. It is shown that this "pi-donor-pi-acceptor" dependence of the singlet-triplet gap is more significant in the case of the nitrenium ions, due to the presence of a positive charge. In addition, it was found that the singlet-triplet gaps decrease with the polarity of the solvent, most likely due to stabilizing electrostatic interactions between the solvent and the charge distribution of the singlet.
引用
收藏
页码:2732 / 2738
页数:7
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