[3+2] versus [2+2] addition of metal oxides across C=C bonds. Reconciliation of experiment and theory

被引：83

作者：

Deubel, DV

Frenking, G

机构：

[1] Univ Marburg, Fachbereich Chem, D-35032 Marburg, Germany

[2] Swiss Fed Inst Technol, Swiss Fed Inst Technol, CSCS, CH-6928 Manno, Switzerland

[3] Acad Sinica, Taipei 115, Taiwan

来源：

ACCOUNTS OF CHEMICAL RESEARCH | 2003年 / 36卷 / 09期

关键词：

D O I：

10.1021/ar020268q

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reaction of a metal oxide with a double bond is the initial step in the osmium-catalyzed cis-dihydroxylation of olefins. The mechanism of the addition of osmium tetraoxide and rhenium(VII) oxides across C=C bonds was controversial. Early work indicated a [3+2] addition, and later kinetic studies suggested an initial [2+2] addition, whereas recent quantum-chemical calculations showed the [3+2] addition to be favored. Experiment and theory have now become reconciled. In this Account, we discuss recent contributions to the mechanistic debate as well as future challenges.

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页码：645 / 651

页数：7

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