Structural effects in the reductive activation of (indenyl)RhL2 complexes: The reduction of [Rh(eta(5)-C9H7)(eta(4)-cod)]

被引：27

作者：

Amatore, C ^{[1
]}

Ceccon, A ^{[1
]}

Santi, S ^{[1
]}

Verpeaux, JN ^{[1
]}

机构：

[1] UNIV PADUA, DIPARTIMENTO CHIM FIS, I-35131 PADUA, ITALY

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 1997年 / 3卷 / 02期

关键词：

electron transfer; indene; kinetics; rhodium;

D O I：

10.1002/chem.19970030217

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reduction of the indenyl complex [Rh(eta(5)-C9H7)(eta(4)-cod)] has been investigated in the context of structural effects induced by the transfer of one electron. The reduction of this complex occurs in two steps, leading first to the radical anion and then to the highly frangible dianion. Both species eliminate the indenyl anion. In the presence of free cyclooctadiene, the related cleavage leading to the indenyl anion and bis-cyclooctadiene rhodium fragments now follows a Michaelis - Menten-type mechanism involving precoordination of one extra COD ligand to the initial radical anion. These results suggest the modification of the hapticity of the indenyl ligand in connection with 17- and 19-electron metal-centered intermediates.

引用

页码：279 / 285

页数：7

共 30 条

[1] ABSOLUTE DETERMINATION OF ELECTRON CONSUMPTION IN TRANSIENT OR STEADY-STATE ELECTROCHEMICAL TECHNIQUES [J].

AMATORE, C ;

AZZABI, M ;

CALAS, P ;

JUTAND, A ;

LEFROU, C ;

ROLLIN, Y .

JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1990, 288 (1-2) :45-63

[2] ECE AND DISPROPORTIONATION .6. GENERAL RESOLUTION - APPLICATION TO POTENTIAL STEP CHRONOAMPEROMETRY [J].

AMATORE, C ;

SAVEANT, JM .

JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1979, 102 (01) :21-40

[3]

AMATORE C, 1978, J ELECTROANAL CHEM, V86, P227, DOI 10.1016/0368-1874(78)87021-X

[4]

AMATORE C, 1989, J ELECTROANAL CHEM, V43, P270

[5]

[Anonymous], 1978, ORGANOMETALLIC MECHA

[6] 19-ELECTRON COMPLEXES AND THEIR ROLE IN ORGANOMETALLIC MECHANISMS [J].

ASTRUC, D .

CHEMICAL REVIEWS, 1988, 88 (07) :1189-1216

[7]

Bard A.J, 1980, Electrochemical methods: Fundamentals and applications

[8]

BORRINI A, 1985, J MOL CATAL, V30, P181, DOI 10.1016/0304-5102(85)80026-2

[9] ON DIFFERENT CHEMICAL AND CATALYTIC BEHAVIOR OF (ETA-INDENYL)-RH(ETA-4-COD) AND CR(CO)3(MU-ETA-ETA-INDENYL)RH(ETA-4-COD) COMPLEXES [J].

CECCON, A ;

GAMBARO, A ;

SANTI, S ;

VENZO, A .

JOURNAL OF MOLECULAR CATALYSIS, 1991, 69 (02) :L1-L6

[10] INDENYL HAPTICITY IN (ETA-INDENYL-RHL2) AND CR(CO)3(MU-ETA-ETA-INDENYL-RHL2) COMPLEXES - A H-1, C-13 AND RH-103 NMR SPECTROSCOPIC STUDY [J].

CECCON, A ;

ELSEVIER, CJ ;

ERNSTING, JM ;

GAMBARO, A ;

SANTI, S ;

VENZO, A .

INORGANICA CHIMICA ACTA, 1993, 204 (01) :15-26

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