Infrared spectroelectrochemistry of [Co3(CPh)(CO)9] in methanol at a platinum electrode

Abstract

In situ infrared spectroelectrochemistry [SNIFTIRS (subtractively normalized interfacial FTIR spectroscopy)] has been used to obtain spectra at a platinum electrode of the reduction products of [Co₃(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 [Co₃(CPh)(CO)₉]^˙–, 50e [Co₃(CPh)(CO)₉]^2– and, tentatively, the 47e [Co₃(CPh)(CO)₈]^– and 49e [Co₃(CPh)(CO)₈L]^˙– were identified and their interrelationships elucidated. Adsorption of the cluster at the surface may be responsible for the unexpected formation of CO₂ upon decomposition of Co(CO)₄^–.