OXIDATIVELY INDUCED ALKYNE ROTATION IN DICOBALT COMPLEXES - STRUCTURAL TESTS OF MOLECULAR-ORBITAL THEORY

被引：39

作者：

AGGARWAL, RP

CONNELLY, NG

CRESPO, MC

DUNNE, BJ

HOPKINS, PM

ORPEN, AG

机构：

来源：

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1992年 / 04期

关键词：

D O I：

10.1039/dt9920000655

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The complexes [Co2(CO)2(mu-RC2R)(mu-dppm)2] 1 (R = Me, Ph or CO2Me; dppm = Ph2PCH2PPh2) undergo reversible one-electron oxidation at a platinum-bead electrode in CH2Cl2; chemical oxidation of 1 with the ferrocenium ion or with iodine gives stable salts of the monocations 1+. The X-ray structures of 1 (R = Me and Ph) show the alkyne bridge to be orthogonal to a cobalt-cobalt bond which is also bridged by the two dppm ligands. The overall structure of 1+ (R = Me), as its [PF6]-salt, is similar but with the alkyne bridge rotated by 12-degrees about an axis perpendicular to the shortened metal-metal bond. The structural changes observed provide direct experimental support for previous bonding studies of the structural preferences of hydrocarbon-bridged M2(CO)6 complexes.

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页码：655 / 662

页数：8

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