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Dynamic stability of carbonyl ylides |
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| Authors: | Akimoto Tachibana Masahiko Koizumi Iwao Okazaki Hiroyuki Teramae Tokio Yamabe |
| Affiliation: | (1) Department of Hydrocarbon Chemistry, Faculty of Engineering, Kyoto University, 606 Kyoto, Japan;(2) Division of Molecular Engineering, Graduate School of Engineering, Kyoto University, 606 Kyoto, Japan;(3) Institute for Fundamental Chemistry, 15 Morimoto-cho, Shimogamo, Sakyo-hu, 606 Kyoto, Japan;(4) Department of Chemistry, University of North Carolina, 27571 Chapel Hill, NC, USA;(5) Film and Film Products Research Laboratories, Toray Industries, Inc., 1-1, 1-chome, Sonayamam, Otsu, 520 Shiga, Japan;(6) NTT Electrical Communications Laboratories, Nippon Telegraph and Telephone Corporation, 3-9-11, Midoricho, Musashino, 180 Tokyo, Japan |
| Abstract: | The non- and fluorine-substituted singlet carbonyl ylides are studied by using ab initio MCSCF calculations. The thermodynamic stability of the carbonyl ylides and the intramolecular stability to isomerization or fragmentation reaction coordinates is demonstrated in terms of the topological structure of the ab initio potential energy surfaces. The allylic resonance is found to be dynamically unstable, considering out-of-plane vibrational mode. The instability is studied by the symmetries of the low-lying excitations out of the MCSCF wave function. |
| Keywords: | Carbonyl ylide Allylic resonance Second-order Jahn Teller effect Reaction coordinate Frontier orbital |
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