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

Abstract

We have previously shown that cyclopentadienyl (Cp[R])-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 Cp[XL] ligands (Cp[XL] = 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.