Electrochemical Dissociative Oxidation of the Unsaturated Pd3(dppm)3(CO)2+ Cluster; An Astonishing Resemblance with the Photo-Oxidative Analogue |
| |
| Authors: | David Brevet Dominique Lucas Yves Mugnier Pierre Harvey |
| |
| Institution: | (1) Laboratoire de Synthèse et Electrosynthèse Organométalliques, CNRS UMR 5188, Faculté des Sciences Mirande, Université de Bourgogne, Allée Savary, 21000 Dijon, France;(2) Département de Chimie, Université de Sherbrooke, Sherbrooke, Québec, Canada, J1K 2R1 |
| |
| Abstract: | Cyclic voltammetry (CV), rotating disk electrode voltammetry (RDE) and bulk electrolysis were used to investigate the electrochemical oxidation of the title cluster in acetonitrile (CH3CN). Two irreversible 2-electron oxidation processes occur at +0.95 V and +1.15 V vs. SCE. Bulk electrolysis demonstrates that the d9–d9 Pd2(dppm)2(NCCH3)
2
2+
4 complex is generated among the first intermediates, and the d8 Pd(dppm)(NCCH3)
2
2+
3 is formed as the final product. The intermediacy of “Pd3(dppm)3(CO)4+” and “Pd3(dppm)
3
4+
” is suspected but not confirmed. This oxidation process exhibits a close resemblance to the photo oxidative reactivity of the title cluster in the presence of chlorocarbons (R–Cl) for which the sole observed product is Pd(dppm)Cl2.This paper is dedicated to Professor Brian Johnson on the occasion of his retirement. |
| |
| Keywords: | Cluster palladium electrochemistry oxidation dissociation |
| 本文献已被 SpringerLink 等数据库收录！ |
|
