STRAINING THE DOUBLE-BOND IN 1,2-DIHYDROXYETHYLENE - A SIMPLE THEORETICAL-MODEL FOR THE ENEDIOL MOIETY IN RUBISCO SUBSTRATE AND ANALOGS

被引:28
作者
ANDRES, J
SAFONT, VS
TAPIA, O
机构
[1] UPPSALA UNIV, DEPT PHYS CHEM, BOX 532, S-75121 UPPSALA, SWEDEN
[2] UNIV JAUME 1, DEPT EXPTL SCI, E-12080 CASTELLO, SPAIN
关键词
D O I
10.1016/0009-2614(92)80037-C
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
The potential energy surfaces for rotation and pyramidalization on the double bond for the singlet ground state and the first triplet state in 1,2-dihydroxyethylene 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 6-31G* basis sets. The premises of a relatively simple electronic mechanism for the (O-3(2)) 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.
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页码:515 / 520
页数:6
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