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

Journal article

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. © 1993 American Chemical Society.

Authors: Compton, R; Barghout, R; Eklund, J; Fisher, A; Bond, A

• Publication status: Published
• Journal: JOURNAL OF PHYSICAL CHEMISTRY
• Volume: 97
• Issue: 8
• Pages: 1661-1664
• Publication date: 1993-02-25
• DOI: 10.1021/j100110a031
• EISSN: 1541-5740
• ISSN: 0022-3654
• Language: English