Activation of a C-H Bond in Indene by [(COD)Rh(μ2-OH)]2

被引：31

作者：

Bercaw, John E. ^{[1
]}

Hazari, Nilay ^{[1
]}

Labinger, Jay A. ^{[1
]}

机构：

[1] CALTECH, Arnold & Mabel Beckman Labs Chem Synth, Pasadena, CA 91125 USA

来源：

ORGANOMETALLICS | 2009年 / 28卷 / 18期

关键词：

COMPLEXES; FUNCTIONALIZATION; RHODIUM(I); MECHANISM; EXCHANGE; OH;

D O I：

10.1021/om9004498

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The air- and water-tolerant hydroxy-bridged rhodium dimer (COD)Rh(mu(2)-OH)](2) cleanly activates the aliphatic C-H bond in indene to generate [(COD)Rh(eta(3)-indenyl)]. The mechanism involves direct coordination of indene to the dimer followed by rate-determining C-H bond cleavage, in contrast to the previously reported analogous reactions of [(diimine)M(mu(2)-OH](2)(2+) (M = Pd, Pt), for which the dimer must be cleaved before rate-determining displacement of solvent by indene. Another difference is observed in the reactions with indene in the presence of acid: the Rh system generates a stable eta(6)-indene 18-electron cation, [(COD)Rh(eta(6)-indene)](+), that is not available for Pd and Pt, which instead form the eta(3)-indenyl C-H activation products. The crystal structure of [(COD)Rh (eta(6)-indene)] is reported.

引用

页码：5489 / 5492

页数：4

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