Mixed platinum-rhodium carbonyl clusters. 1. Synthesis, reactivity, and solution structures of [PtRh5(CO)15]-, [PtRh4(CO)14]2- and [PtRh4(CO)12]2-

Abstract

The reductive carbonylations of mixtures of Na2PtC16 and RhC13.xH20 (at room temperature and 1 atm CO) are reported. From the reaction mixtures [PtRh5(CO)15]- and [PtRh4(CO)14]2- have been isolated; the latter is in equilibrium, through the release and absorption of CO, with [PtRh4(CO)12]2-. Solution structures and fluxional behavior of all these anions have been established by multinuclear (13C, 13C-{103Rh}, 103Rh, 195Pt) variable-temperature NMR measurements.