SPECTRAL CHARACTERIZATION OF INTERMEDIATES IN PHOTOCHEMICAL AND DARK REACTIONS OF HEXANUCLEAR RHODIUM CLUSTERS

Irradiation of Rh6(CO)16 in chloroform and dichloromethane at ambient temperature (lambda(irr)>300 nm) affords loss of one CO as the only IR detectable photoreaction to yield a product formulated as Rh6(CO)15S (S = CHCl3, CH2Cl2), where the solvent occupies one of the twelve terminal positions in the structure of the parent cluster. Kinetics of the Rh6(CO)15S reaction with CO have been studied. Species of the same nature were shown to be formed in dark reactions: Rh6(CO)16+Me3NO --> S Rh6(CO)15S+CO2+Me3N; Rh6(CO)15MeCN --> S Rh6(CO)15S+MeCN; Rh6(CO)16 --> S Rh6(CO)15S+CO.