Photosynthetic organisms catalytically oxidize water to dioxygen using an oxo-bridged Mn4-Ca cluster called the Oxygen Evolving Complex (OEC) located within the Photosystem II protein. The manganese metal centers are high valent Mn(IV) and Mn(V) when water oxidation occurs. Our goal is to modify and oxidize manganese clusters previously prepared by the Zdilla group with initial focus on Mn(OPhPh2)2(Et2O)2 and Mn3(�-OPhPh2)4(NR2)2(THF)2 (R = Me3Si), in which metal atoms are low-valent Mn(II), but biologically active manganese, like those found in the OEC occur in higher oxidation states. Oxidation of these clusters was explored using techniques of ligand exchange and oxygen transfer with focus on labile, non-chelating ligands in order to promote reactivity. Oxidized ligand byproducts were observed from the reaction of the monomer with oxidants. Reactions of the trimer have led to a variety of strongly colored products under various conditions. The products from the trimer oxidations will be characterized and presented.

Novel synthesis of high-valent and low-coordinate manganese clusters

244th National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.