The mixed-metal carbonyl cluster anion [Ru₃Ir(CO)₁₃]^– : synthesis, molecular structure, fluxionality, reactivity

摘要

The new cluster anion [RuIr(CO)] was synthesized in high yield from [Ru(CO)] and [Ir(CO)]. The single-crystal X-ray structure analysis of the bis(triphenylphosphoranylidene)ammonium salt revealed the presence of two isomers, [RuIr(CO)(µ-CO)] and RuIr(CO)(µ-CO)] in the same crystal. Both and present a tetrahedral RuIr framework, differing only by the number of bridging carbonyl ligands. Variable-temperature C NMR spectroscopic studies of revealed the fluxionality of the carbonyl ligands and the interconversion of both isomers in solution. Protonation of gave the neutral cluster [HRuIr(CO)] , whereas reaction of with molecular hydrogen yielded the anion [HRuIr(CO)]. Either hydrogenation of or protonation of gave [HRuIr(CO)] . The tetrahedral structure of the hydrido derivatives was confirmed by a single-crystal X-ray structure analysis of the bis(triphenylphosphoranylidene)ammonium salt of .