Hilal R, el-Aaser A M
Biophys Chem. 1985 Aug;22(3):145-50. doi: 10.1016/0301-4622(85)80036-3.
The electronic structures of methyl acetate and S-methyl thioacetate and the corresponding anions have been investigated using the INDO-MO method. Equilibrium geometries, gas-phase anion proton affinities and barriers to internal rotation have been computed. Analysis of the effect of the d-type functions on sulfur on the static and dynamic properties of the thioester and its anion reveal no role for (p-d) pi conjugative effects. The results of this work indicate that the unique properties of thioester, and hence esters of coenzyme A, may be attributed to the lack of resonance, rather than to a sulfur d-orbital expansion.
采用INDO-MO方法研究了乙酸甲酯和硫代乙酸甲酯及其相应阴离子的电子结构。计算了平衡几何结构、气相阴离子质子亲和能和内旋转势垒。对硫原子上d型函数对硫酯及其阴离子的静态和动态性质的影响进行分析，结果表明不存在（p-d）π共轭效应。这项工作的结果表明，硫酯以及辅酶A酯的独特性质可能归因于缺乏共振，而非硫d轨道扩展。
