Nucleophilic attack at selenium in diselenides and selenosulfides. A computational study

被引：79

作者：

Bachrach, SM ^{[1
]}

Demoin, DW ^{[1
]}

Luk, M ^{[1
]}

Miller, JV ^{[1
]}

机构：

[1] Trinity Univ, Dept Chem, San Antonio, TX 78212 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2004年 / 108卷 / 18期

关键词：

D O I：

10.1021/jp037972o

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：

Nucelophilic substitution at selenium is examined using the B3LYP and MP2 methods. Various nucleophiles (HS-, CH3S-, HSe-, and CH3Se-) and substrates (R1SSeR2 and R1SeSeR2 with R-1 and R-2 = H or Me) are used to model substitution at selenium in diselenides and selenosulfides. In all cases, the mechanism is addition-elimination. A stable hypercoordinate selenium intermediate lies in a well that is 8-14 kcal mol(-1) deep. Nucleophilic attack at selenium is both kinetically and thermodynamically more favorable than at sulfur.

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页码：4040 / 4046

页数：7

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