ORGANOMETALLIC PHOTOELECTROCHEMISTRY - OXIDATION OF FAC-TRICARBONYLCHLORO[BIS(DIPHENYLPHOSPHINO)METHANE]MANGANESE(I)

被引：35

作者：

COMPTON, RG ^{[1
]}

BARGHOUT, R ^{[1
]}

EKLUND, JC ^{[1
]}

FISHER, AC ^{[1
]}

BOND, AM ^{[1
]}

COLTON, R ^{[1
]}

机构：

[1] LA TROBE UNIV,DEPT CHEM,BUNDOORA,VIC 3083,AUSTRALIA

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1993年 / 97卷 / 08期

关键词：

D O I：

10.1021/j100110a031

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The electrochemical oxidation of fac-tricarbonylchloro[bis(diphenylphosphino)methane]manganese(I) (FCM) has been studied at an irradiated (390-nm) channel electrode. Photocurrent measurements made as a function of variable mass transport, combined with simultaneous photoelectrochemical ESR measurements, have shown that new electrode reaction pathways appear under illumination. Specifically, first, light can induce a fac to mer isomerization in the molecule which leads to oxidation at potentials lower than those required in the dark, and this process has been quantitatively interpreted as a photo-CE (C = chemical step; E = electrode step) mechanism. Second, the direct oxidation of FCM is modified under illumination with enhancement of the current flowing. A modified disproportionation mechanism was found to uniquely and quantitatively describe the process. In both cases the relevant rate constants are reported.

引用

页码：1661 / 1664

页数：4

共 10 条

[1] KINETIC AND THERMODYNAMIC STUDY OF REACTIONS OF SOME SUBSTITUTED MANGANESE(I) AND MANGANESE(II) TRICARBONYL COMPLEXES USING SPECTROPHOTOMETRIC AND ELECTROCHEMICAL TECHNIQUES [J].