SELECTIVE GENERATION OF VARIOUS RHODIUM CARBONYL CLUSTER ANIONS IN AMINATED POLYMERS AND THEIR CATALYSTS FOR THE WATER-GAS SHIFT REACTION AND DEOXYGENATION OF VARIOUS N-O BONDS

Aminated polystyrenes were prepared by amination of chloromethylated polystyrenes. Several Rh carbonyl cluster anions could be selectively generated in the aminated polymer with use of Rh6(CO)16. The reaction of Rh6(CO)16 with the aminated polystyrenes at 40-degrees-C under 6 atm of CO gave a dark green polymer involving [Rh6(CO)15H]- and [Rh6(CO)15]2-, while [Rh14(CO)25]4- was formed in the polymers at 100-degrees-C. Treatment of the Rh6 anion species with aqueous KOH solution gave a polymer-bound [Rh7(CO)16]3- complex. The Rh6 anion species were catalytically active for the deoxygenation of N-O bonds, e.g., conversion of aliphatic nitro compounds to nitriles, N-oxides to amines, and hydroxylamines to amines. Rh14 species could be observed in the water-gas shift reaction. These isolated polymer-bound Rh carbonyl anion complexes were found to be reusable as catalysts for the above reactions.