COPPER-DIOXYGEN COMPLEXES - FUNCTIONAL MODELS FOR PROTEINS

The complex [(TMPA)Cu-I(RCN)](+) (1) (TMPA = tris[(2-pyridyl)methyl]am ine) binds O-2 forming [ {(TMPA)Cu}(2)(O-2)](2+) (2), with trans-mu-1, 2 peroxo-coordination. Study of complexes with binucleating ligand an alogues provide considerable insights and achievement of room-temperat ure solution stability. Binucleating ligands with tridentate bis[(2-py ridyl)ethyl]amine chelates give side-on mu-eta(2):eta(2)- peroxo dicop per(II) complexes, likewise in a monooxygenase model system. (P)FeX-Cu (L) (P = porphyrinate or binucleating tethered porphyrin; X = O2-, OH- ) oxidized resting state models of the heme a(3) and Cu-B site of cyto chrome c oxidase have been generated and characterized, and reduced (P )Fe-II/Cu-I compounds, for O-2 reactivity studies, have been synthesiz ed. A heme/non-heme diiron complex has been generated as a possible mo del for NO reductase.