Hydrotris(pyrazolyl)borate metallacycles: Conversion of a late-metal metallacyclopentene to a stable metallacyclopentadiene-alkene complex

被引：32

作者：

O'Connor, JM ^{[1
]}

Closson, A ^{[1
]}

Gantzel, P ^{[1
]}

机构：

[1] Univ Calif San Diego, Dept Chem & Biochem, La Jolla, CA 92093 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2002年 / 124卷 / 11期

关键词：

D O I：

10.1021/ja0255296

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The bis(ethene) complex [(Tp)Ir(C2H4)2] (3) undergoes reaction with dimethyl acetylenedicarboxylate (DMAD) in acetonitrile solvent at 60 °C to give the trispyrazolylborate metallacyclopent-2-ene complex [(Tp)Ir{CH2CH2C(CO2Me)=C(CO2Me)}(NCMe)] (4). Spectroscopic analysis of a room-temperature reaction between 3 and DMAD in acetonitrile-d3 provides evidence for the formation of an η2-alkene/η2-alkyne intermediate on the path to 4. The reaction of 3 with DMAD in THF solvent leads to the formation of the THF-ligated metallacyclopent-2-ene complex [(Tp)Ir{CH2CH2C(CO2Me)=C(CO2Me)}(THF)] (5), which undergoes further reaction with DMAD at 60 °C in benzene to give [(Tp)Ir{C(CO2Me)=C(CO2Me)=C(CO2Me)=C(CO2Me)}(η2-CH2=CH2)] (6). Complex 4 was structurally characterized by X-ray crystallography. Copyright © 2002 American Chemical Society.

引用

页码：2434 / 2435

页数：2

共 32 条

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