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

•Trinuclear mixed-valence paramagnetic manganese carbonyls with dithiolates were prepared.•All three manganese centers in each complex present octahedral geometry. No metal–metal bonds were present.•The complexes were prepared under mild conditions, in short reaction times, and in good yields.•Sound characterization of the complexes by spectroscopic techniques and an X-ray analysis was achieved.

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.

Graphical abstractMixed-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. No metal–metal bonds exist in these trinuclear species; one manganese atom exhibits a formal oxidation state of +4; while the other two possess an oxidation state of +1.Figure optionsDownload full-size imageDownload as PowerPoint slide