Theoretical characterization of the mechanism of Hg-C bond cleavage by halogenic acids

被引：20

作者：

Barone, V ^{[1
]}

Bencini, A ^{[1
]}

Totti, F ^{[1
]}

Uytterhoeven, MG ^{[1
]}

机构：

[1] UNIV FLORENCE,DIPARTIMENTO CHIM,I-50144 FLORENCE,ITALY

来源：

ORGANOMETALLICS | 1996年 / 15卷 / 05期

关键词：

D O I：

10.1021/om9508391

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Ab initio calculations at the MP2 level show that the CH3-Hg bond is broken by halogenic acids by a one-step mechanism, proceeding through a closed transition state in which, however, bond forming and breaking are not completely synchronous. Activation energies closely parallel Hg-C bond strengths and are strongly influenced by the electronegativity of the ligands bound to Hg. For instance, the energy barrier decreases by roughly 50% on going from CH3HgCl to CH3HgCH3. The general agreement between computed and experimental trends gives further support to the reaction mechanism.

引用

页码：1465 / 1469

页数：5