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

Dirk V. Deubel; Gernot Frenking

doi:10.1021/ar020268q

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

Dirk V. Deubel, Gernot Frenking

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Abstract

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.

Original language	English
Pages (from-to)	645-651
Number of pages	7
Journal	Accounts of Chemical Research
Volume	36
Issue number	9
DOIs	https://doi.org/10.1021/ar020268q
State	Published - 1 Sep 2003
Externally published	Yes

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abstract = "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.",

author = "Deubel, {Dirk V.} and Gernot Frenking",

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AU - Frenking, Gernot

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N2 - 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.

AB - 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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M3 - 文章

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JO - Accounts of Chemical Research

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ER -

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

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