Thermal reactivity of Group 9 transition metal pinacolate complexes: heterocumulene cleavage and C-O bond formation

被引：9
|
作者：
Holland, AW
Bergman, RG [1 ]
机构：
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
[2] Univ Calif Berkeley, Ctr New Direct Organ Synth, Berkeley, CA 94720 USA
来源：
INORGANICA CHIMICA ACTA | 2002年 / 341卷
基金：
美国国家科学基金会;
关键词：
metal glycolate; alkoxide complexes; rhodium; iridium; heterocumulene; insertion reactions;
D O I：
10.1016/S0020-1693(02)01234-3
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The reactions of Group 9 transition metal pinacolate complexes Cp*M(pin) (M = Co (1), Rh (2), Ir (3)) with heterocumulenes (Y=C=Z) are described. In these transformations the C=Z bond of the heterocumulene is cleaved, and the pinacolate ligand is incorporated into an organic heterocycle (pin)C=Y. In some cases a clean organometallic product of the general formula Cp*MZ(2)C=Y is also produced. The regiochemistry of these reactions has been explored and found to follow expected trends, and evidence suggests a mechanism involving initial heterocumulene insertion into an M-O bond yielding a 7-membered metallacycle, followed by 1,2 elimination. (C) 2002 Elsevier Science B.V. All rights reserved.
引用
收藏
页码：99 / 106
页数：8
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