Linkage Isomerization Reactions of M(CO)2L Complexes (M = (η5-C5H5)Mn, (η5-C5H5)Re, or (η6-C6H6)Cr; L=2,3-Dihydrofuran): A Step-Scan FTIR and DFT Study

被引：8

作者：

Bengali, Ashfaq A. ^{[1
]}

Hall, Michael B. ^{[2
]}

Wu, Hong ^{[2
]}

机构：

[1] Texas A&M Univ, Dept Chem, Doha, Qatar

[2] Texas A&M Univ, Dept Chem, College Stn, TX 77843 USA

来源：

ORGANOMETALLICS | 2008年 / 27卷 / 22期

关键词：

D O I：

10.1021/om800457d

中图分类号：

O61 [无机化学];

学科分类号：

070301 [无机化学]; 081704 [应用化学];

摘要：

The linkage isomers, M(CO)(2)-(eta(1)-(O)-2,3 DHF) and M(CO)(2)-(eta(2)-(C,C)-2,3 DHF) [M = (eta(5)-C5H5)Mn, (eta(5)-C5H5)Re, (eta(6)-C6H6)Cr; DHF = dihydrofuran] are formed upon photolysis of the parent M(CO)(3) complexes in the presence of 2,3-DHF. The rearrangement of the oxygen bound to the thermodynamically favored a bound complex is followed on the millisecond to microsecond time scale using step-scan FTIR. The rate of the isomerization reaction increases in the order Re < Mn < Cr primarily due to a decrease in the activation enthalpy. The experimental data along with theoretical calculations suggest that the rearrangement proceeds intramolecularly in which the metal migrates from one functional group to another.

引用

页码：5826 / 5829

页数：4

共 31 条

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