Direct observation of a 14-electron ruthenacyclobutane relevant to olefin metathesis

被引：155

作者：

Romero, PE ^{[1
]}

Piers, WE ^{[1
]}

机构：

[1] Univ Calgary, Calgary, AB T2N 1N4, Canada

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2005年 / 127卷 / 14期

关键词：

D O I：

10.1021/ja042259d

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The 14-electron ruthenium phosphonium alkylidene complex [(IH2Mes)Cl2Ru=CH(PCy3)][B(C6F5)4], 1b, a highly active olefin metathesis catalyst, reacts with stoichiometric quantities of ethylene at -50 °C in CD2Cl2 to generate the ruthenacyclobutane complex [(IH2Mes)Cl2RuCH2CH2CH2], 2, and [CH2=CH(PCy3)][B(C6F5)4] in quantitative yield by NMR spectroscopy. 1H and 13C NMR spectroscopies on 2 and 2-13C3 are consistent with a symmetrical C2v structure, providing the first experimental information concerning this crucial intermediate in ruthenium-mediated olefin metathesis. At -50 °C, exchange with free ethylene takes place on the chemical time scale. Complex 2 decomposes in solution upon warming to room temperature, generating propene and unknown ruthenium product(s). Copyright © 2005 American Chemical Society.

引用

页码：5032 / 5033

页数：2

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