Synthesis of mixed-valence trinuclear carbonylmanganese dithiolates: Promoting vacant coordination sites in tricarbonyl[(1-5-η)-pentadienyl]manganese

Mixed-valence complexes Mn3(CO)6(μ-S(CH2)nS-κ2-S,S′)3n = 2, 3, and 4 were prepared upon reaction of tricarbonyl[(1-5-η)-pentadienyl]manganese with the respective alkanedithiols at room temperature in good yields. The three metal centers are bound by thiolate bridges with no metal–metal bonds; one manganese atom exhibits a formal oxidation state of +4; while the other two possess an oxidation state of +1. EPR and X-ray analysis showed an octahedral environment around the manganese centers.