Copperdioxygen complexes: Functional models for proteins

The complex [(TMPA)CuI(RCN)] + (1) (TMPA = tris[(2-pyridyl)methyl]amine) binds 0 2 forming [ ((TMPA)Cu]2(02)]2+ (2), with truns-p-l,2 peroxo-coordination. Study of complexes with binucleating ligand analogues provide considerable insights and achievement of room-temperature solution stability. Binucleating ligands with tridentate bis[(2-pyridyl)ethyl]amine chelates give side-on p-q2:q2peroxo dicopper(I1) complexes, likewise in a monooxygenase model system. (P)FeX-Cu(L) (P = porphyrinate or binucleating tethered porphyrin; X = 02, OH-) oxidized resting state models of the heme a3 and CUB site of cytochrome c oxidase have been generated and characterized, and reduced (P)FeII/Cul compounds, for 0 2 reactivity studies, have been synthesized. A hemehon-heme diiron complex has been generated as a possible model for NO reductase.