Anodically-induced metal deprotonation of the hydride complexes [{PCH2CH2PPh2)(3)}M(H)Cl] (M=Fe, Ru, Os): The first step to the electrogeneration of Fe(I), Ru(I) and Os(I) five-coordinate complexes

被引：25

作者：

Bianchini, C ^{[1
]}

Peruzzini, M ^{[1
]}

Ceccanti, A ^{[1
]}

Laschi, F ^{[1
]}

Zanello, P ^{[1
]}

机构：

[1] UNIV SIENA,DIPARTIMENTO CHIM,I-53100 SIENA,ITALY

来源：

INORGANICA CHIMICA ACTA | 1997年 / 259卷 / 1-2期

关键词：

hydride complexes; electrochemistry; iron complexes; ruthenium complexes; osmium complexes; ESR spectroscopy;

D O I：

10.1016/S0020-1693(96)05585-5

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The electrochemical behaviour of the (hydride)chloride complexes [(PP3)M(H)Cl] (M = Fe, Ru, Os) has been studied by cyclic voltammetry and controlled-potential electrolysis in tetrahydrofuran (PP3 = P(CH2CH2PPh2)(3)). All compounds undergo anodically-induced deprotonation to give the corresponding M(II) chlorides [(PP3)MCl](+). All the oxidation processes correspond to an EEC reaction pathway. The two-electron oxidation processes occur at coincident potentials for M = Ru, at slightly different potentials for M = Os, and at largely different potentials for M = Fe. The M(II) complexes [(PP3)MCl](+) are reversibly reduced to the corresponding M(I) derivatives [(PP3)MCl], which can be generated in solution by exhaustive macroelectrolysis. The paramagnetic Fe(I), Ru(I) and Os(I) chloride complexes have been characterised by X-band ESR spectroscopy in glassy and fluid solutions.

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页码：61 / 70

页数：10

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