MECHANISTIC STUDY OF PHOTOELECTROCHEMICAL REACTIONS - PHOTO-TRANSIENTCHARACTERIZATION OF CE PROCESSES

A channel electrode photo-transient experiment is described for the me chanistic characterization of photo-CE processes. This involves monito ring the transport limited current due to the discharge of a photo-gen erated electroactive species immediately following the stepwise applic ation of light to the system. The theory of the experiment is given an d a working surface presented which allows the analysis of experimenta l transients regardless of the cell geometry or solution flow rate use d in their measurement. The approach is applied to the photo-electroch emical oxidation of the aminocarbene complex (eta(5)-C5H5)Fe(CO){P(p-T ol)(3)}{=C(NHMe)(Me)}]BF4 in acetonitrile solution at a platinum elect rode. The process, in the presence of light of wavelengths near 330 nm , is confirmed to be of the photo-CE type.