Brunner, Henri and Ikeshita, Masahiro and Tsuno, Takashi (2024) The Pyramidalization of sp²Centers in 3/2-Systems Is a "Structural Breathing" Independent of Energy. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 27 (44). ISSN 1434-193X, 1099-0690
Full text not available from this repository. (Request a copy)Abstract
In 3/2-systems, such as the acetate anion H3C alpha C ' OO-, an sp(3) center and an sp(2) center are connected by a covalent bond. The interaction of threefold and twofold symmetry results in the pyramidalization of the sp(2 )center during rotation about bond E-sp3-E-sp2. Rotation angles psi=0 degrees, +/- 60 degrees, +/- 120 degrees, and +/- 180 degrees account for conformations with a symmetry plane containing the planar sp2 center C alpha C ' OO. However, in all conformations with rotation angles psi not equal 0 degrees, +/- 60 degrees, +/- 120 degrees, and +/- 180 degrees this symmetry plane is lost and pyramidalization must occur with maxima at rotation angles psi=+/- 30 degrees, +/- 90 degrees, and +/- 150 degrees, because the two sides of the sp(2) center C alpha C ' OO are different. Inevitably, this leads to a pyramidalization/rotation profile theta/psi with three maxima, three minima, and six zero-crossings. Thus, myriads of 3/2-compounds pyramidalize their sp2 centers each moment to the order of about 2 degrees in a coupled pyramidalization/rotation molecular motion independent of energy.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | DISTORTION; sp2 centers; Pyramidalization; Coupled intramolecular motion; Structural breathing; DFT calculations |
| 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: | 03 Dec 2025 06:55 |
| Last Modified: | 03 Dec 2025 06:55 |
| URI: | https://pred.uni-regensburg.de/id/eprint/64185 |
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