Density functional theory gas- and solution-phase study of nucleophilic substitution at di- and trisulfides
Density functional theory gas- and solution-phase study of nucleophilic substitution at di- and trisulfides
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DOI：
10.1007/s00214-002-0323-4
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发表时间：
2002-05-01
影响因子：
1.7
通讯作者：
Mynar, JL
中科院分区：
文献类型：
--
作者：
Bachrach, SM;Hayes, JM;Mynar, JL
密度泛函计算表明，硫酸-二硫化物和硫酸-三硫化物交换反应中的亲核取代是通过加成-消除途径进行的。溶液计算采用B3LYP/6-31 + G*和极化连续体方法。这些溶液相计算表明，对于受攻击的硫携带氢原子的反应，取代是通过加减机制进行的；然而，当一个甲基连接到被攻击的硫上时，可以预测S(N)2机制。
Density functional calculations indicate that nucleophilic substitution in the thiolate-disulfide and thiolate-trisulfide exchange reactions proceeds by an addition-elimination pathway. Solution calculations were performed using B3LYP/6-31 + G* and the polarized continuum method. These solution-phase calculations indicate that for the reactions where the sulfur under attack bears a hydrogen atom, the substitution proceeds via an addition-elimination mechanism; however, when a methyl group is attached to the sulfur under attack, the S(N)2 mechanism is predicted.