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Abstract:
The first carbonyl RhMn cluster Na2[Rh3Mn3(CO)18] 2 has been synthesized and structurally characterized, resulting from the salt metathesis reaction of RhCl3 with Na[Mn(CO)5] 1 in 49% isolated yield. The dianionic Rh3Mn3 cluster core of 2 can serve as a molecular single‐source precursor (SSP) for the low temperature preparation of selective high‐performance RhMn catalysts for the conversion of syngas to ethanol (StE). Impregnation of 2 on silica (davisil) led to three different silica‐supported RhMnOx catalysts with dispersed Rh nanoparticles tightly surrounded by a MnOx matrix. With ethanol selectivities of up to 24.1%, the Rh3Mn3 cluster precursor‐derived catalysts show the highest reported selectivity and performance in the conversion of StE for silica‐supported RhMnOx catalysts.