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

Mixed-valence complexes Mn-3(CO)(6)(mu-S(CH2)(n)S-kappa(2)-S,S')(3) n = 2, 3, and 4 were prepared upon reaction of tricarbonyl[(1-5-eta)-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. (C) 2013 Elsevier B.V. All rights reserved.