title: Toward synthetic analogues of linked redox and catalytic multimetal sites in proteins: a model of the histidine-cysteine bridged dicopper array.
abstract: Contiguous HisCys residues link a type 1 Cu electron-transfer site to a catalytic Cu-containing site in nitrite reductase and the multicopper oxidases. In efforts to understand the role of the linker in these multimetallic arrays and to design new catalysts, a mixed-valent dicopper complex comprising a bridging thiolate/N-donor ligand that models the CuHisCysCu motif was prepared and characterized by X-ray crystallography. Comparison of spectroscopic and cyclic voltammetry data to those of the mononuclear analogues of each portion of the complex, LCuSCPh(3) and LCu(py) (L = beta-diketiminate, py = pyridyl), confirmed retention of the dicopper structure in solution.
authors.affiliation: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455, USA.
authors.forename: Way-Zen
authors.initials: WZ
authors.lastname: Lee
authors.forename: William B
authors.initials: WB
authors.lastname: Tolman
mesh_terms: D001665:Binding Sites; D001952:Bridged-Ring Compounds / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003553:Cystine / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D006639:Histidine / Q000737:chemistry*; D007202:Indicators and Reagents; D008024:Ligands; D008670:Metals / Q000737:chemistry*; D010084:Oxidation-Reduction; D010088:Oxidoreductases / Q000737:chemistry; D011506:Proteins / Q000737:chemistry*
chemical_list: D001952:Bridged-Ring Compounds; D007202:Indicators and Reagents; D008024:Ligands; D008670:Metals; D011506:Proteins; D003553:Cystine; D006639:Histidine; D003300:Copper; D010088:Oxidoreductases