CO Binding onto Heterometals of [Mo₃S₄M] (M = Fe, Co, Ni) Cubes

We have previously shown that cyclopentadienyl (CpR)-supported [Mo3S4] platforms capture and stabilize halides of hetero-metals (M) under reducing conditions to give [Mo3S4M] cubes. Here we report Co and Ni variants with CpXL ligands (CpXL = C5Me4SiEt3) and CO binding to the [Mo3S4M] clusters (M = Fe, Co, Ni). Properties of the isolated CO-bound [Mo3S4M] cubes were investigated by X-ray diffraction, IR, and electrochemical analyses. Density functional theory (DFT) calculations were performed for the isolated CO-bound clusters to evaluate M-CO interactions. These analyses constitute foundations to develop bio-mimetic molecular catalysts for the direct conversion of CO and/or CO2 into hydrocarbons, which can contribute to the reduction of carbon emissions.