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Straining the double bond in 1,2-dihydroxyethylene. A simple theoretical model for the enediol moiety in Rubisco's substrate and analogs

✍ Scribed by J. Andrés; V.S. Safont; O. Tapia


Publisher
Elsevier Science
Year
1992
Tongue
English
Weight
520 KB
Volume
198
Category
Article
ISSN
0009-2614

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✦ Synopsis


The potential energy surfaces for rotation and pyramidalization on the double bond for the singlet ground state and the first triplet state in 1 ,Zdihydroxyethylene are calculated with the ab initio molecular orbital method. Full geometry optimizations are carried out at the HF-SCF including MP2 level of theory with 6-3 lG* basis sets. The premises of a relatively simple electronic mechanism for the ('0,) oxygenation reaction on a strained enediol are obtained. The idea is based on the fact that the energy gap between the singlet and first triplet state of a dienol moiety decreases to a small value where excitation to the triplet state may be induced by oxygen.