Brunner, Henri and Ikeshita, Masahiro and Tsuno, Takashi (2021) Rotation about a Covalent Bond and Pyramidalization of an Adjacent sp(2) Center are a Synchronized Molecular Motion. JOURNAL OF ORGANIC CHEMISTRY, 86 (15). pp. 10420-10426. ISSN 0022-3263, 1520-6904
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The correlation of the rotation about the C-alpha-C' bond and the pyramidalization of the sp(2)-hybridized carbon atom C' and its three bonding partners to a flattened tetrahedron in the substructure C-beta-C alpha H-C'(=O)-OMe of substituted methyl acetates revealed that the two processes are not independent of each other but parts of a common molecular motion, as outlined in the preceding back-to-back paper. In the present study, we generalized the substructure to X-beta-C alpha H-C'(=Y)-Z with X, Y, and Z = O, N, C, and S, extending the analysis to several hundred thousand structures of the type carboxylates, carboxamides, ketones, imines, olefins, peptides, lactates, carbothioates, and phenyl derivatives, retrieved from the Cambridge Structural Database. psi/theta Scatter plots of the individual structure points and their averaging in psi/theta(av) curves result in wavelike patterns with three maxima and minima and inversion symmetry at psi = 0 degrees and +/- 180 for a 360 degrees rotation of C-beta about the C-alpha-C' bond. The pyramidalization of the sp(2)-hybridized group C alpha CiCoCo', which is part of the aromatic system, even disturbs the planarity of phenyl rings. Density functional theory calculations confirm the results of the CSD search.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CAMBRIDGE STRUCTURAL DATABASE; AB-INITIO; DISTORTION; DFT |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Alumni or Retired Professors > Prof. Dr. Henri Brunner |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 17 Aug 2022 11:58 |
| Last Modified: | 17 Aug 2022 11:58 |
| URI: | https://pred.uni-regensburg.de/id/eprint/46637 |
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