Mechanism of the electrochemical oxidation of zero valent palladium complexes

被引：18

作者：

Amatore, C

Jutand, A

Medeiros, MJ

Mottier, L

机构：

[1] Ecole Normale Supérieure, Département de Chimie, URA CNRS 1679, F-75231 Paris Cedex 5

[2] Departamento de Quimica, Universidade do Minho, P-4719 Braga Codex, Largo do Paço

来源：

JOURNAL OF ELECTROANALYTICAL CHEMISTRY | 1997年 / 422卷 / 1-2期

关键词：

palladium complexes; oxidation; mechanism; valence;

D O I：

10.1016/S0022-0728(96)04901-7

中图分类号：

O65 [分析化学];

学科分类号：

070302 ; 081704 ;

摘要：

Within long times scales, the electrochemical oxidation of Pd(O)(PPh3)(4) proceeds through an ECE-like two-electron process to afford two cationic palladium(II) complexes in equilibrium: Pd(II)(PPh3)(2)(BF4)(2) and Pd(II)(PPh3)(3)(BF4)(2), whose relative concentrations depend on the triphenylphosphine concentration. At short time scales, one-electron oxidation affords a transient cationic palladium(I) complex involved in a fast follow-up endergonic equilibrium which is believed to consist in a geometrical rearrangement (tetrahedral to square planar), most probably induced by the solvent.

引用

收藏

页码：125 / 132

页数：8

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