INFRARED SPECTROELECTROCHEMISTRY OF [CO-3(CPH)(CO)(9)] IN METHANOL ATA PLATINUM-ELECTRODE

In situ infrared spectroelectrochemistry [SNIFTIRS (subtractively norm alized interfacial FTIR spectroscopy)] has been used to obtain spectra at a platinum electrode of the reduction products of [Co-3(CPh)(CO)(9 )] in absolute methanol, in CO saturated methanol, in the presence of a ligand [P(C6H4SO3-m)(3)](3-) (L) and in dichloromethane. The cluster species 49e [Co-3(CPh)(CO)(9)](.-), 50e [Co-3(CPh)(CO)(9)](2-) and, t entatively, the 47e [Co-3(CPh)(CO)(8)](-) and 49e [Co-3(CPh)(CO)(8)L]( .-) were identified and their interrelationships elucidated. Adsorptio n of the cluster at the surface may be responsible for the unexpected formation of CO2 upon decomposition of Co(CO)(4)(-).