VOLTAMMETRIC STUDY OF THE PHOTOLYSIS OF FAC-TRICARBONYL-ETA(3)-(BIS[2-(DIPHENYLPHOSPHINO)ETHYL]PHENYLPHOSPHINE)MOLYBDENUM

Voltammetric studies at a channel electrode irradiated with monochromatic visible light have been carried out to demonstrate that the photolysis of fac-Mo(CO)3{η3-[(Ph2PCH2CH 2)2PPh]}† in acetonitrile or dimethylformamide solution leads to the formation of the corresponding mer-isomer. No photofragmentation resulting in the loss of carbon monoxide or phosphine is observed on the voltammetric timescale. Kinetic parameters for the photo-isomerisation are reported

Voltammetric monitoring of photochemical reactions: Photo-induced electron transfer to p-chloronitrobenzene

Channel electrode voltammetry using an irradiated gold electrode is used to study the photolysis of p-chloronitrobenzene in aqueous ethanolic solution in the presence of the hydroxide anion. The formation of the stable radical anion, [p-ClC6H4NO2]•-, via light-induced electron transfer is demonstrated and kinetic parameters are reported

VOLTAMMETRIC STUDY OF THE PHOTOLYSIS OF FAC-TRICARBONYL-ETA(3)-(BIS[2-(DIPHENYLPHOSPHINO)ETHYL]PHENYLPHOSPHINE)MOLYBDENUM

Voltammetric studies at a channel electrode irradiated with monochromatic visible light have been carried out to demonstrate that the photolysis of fac-Mo(CO)3{η3-[(Ph2PCH2CH 2)2PPh]}† in acetonitrile or dimethylformamide solution leads to the formation of the corresponding mer-isomer. No photofragmentation resulting in the loss of carbon monoxide or phosphine is observed on the voltammetric timescale. Kinetic parameters for the photo-isomerisation are reported

PHOTOELECTROCHEMICAL OXIDATION OF TRIS(DIMETHYLDITHIOCARBAMATO-S,S')COBALT(III)

The electro-oxidation of tris(dimethyldithiocarbamato-S,S′)cobalt(III), [Co(S2CNMe2)3], at platinum electrodes in acetonitrile solution in the presence of light of wavelengths between 300 and 600 nm gave rise to appreciable photocurrents. These are suggested to arise from an absorption of light by the one-electron oxidation product [Co(S2CNMe2)3]+ which is followed by an internal redox reaction which leads to the fragmentation of the cation and the probable formation of [Co(S2CNMe2)2] and oxidised ligand. Kinetic parameters have been obtained for the decomposition of [Co(S2CNMe2)3]+ in the presence of light. In the absence of light the cation undergoes a rate-determining dimerisation reaction which is followed by an internal redox reaction which leads to the formation of [Co2(S2CNMe2)5]+; at light intensities of ca. 10 mW cm-2 both pathways are kinetically significant and the electrode reaction consists of parallel electrodimerisation and photofragmentation pathways