title: A N3S(thioether)-ligated Cu(II)-superoxo with enhanced reactivity.
abstract: Previous efforts to synthesize a cupric superoxide complex possessing a thioether donor have resulted in the formation of an end-on trans-peroxo-dicopper(II) species, [{(Ligand)Cu(II)}2(μ-1,2-O2(2-))](2+). Redesign/modification of previous N3S tetradentate ligands has now allowed for the stabilization of the monomeric, superoxide product possessing a S(thioether) ligation, [((DMA)N3S)Cu(II)(O2(•-))](+) (2(S)), as characterized by UV-vis and resonance Raman spectroscopies. This complex mimics the putative Cu(II)(O2(•-)) active species of the copper monooxygenase PHM and exhibits enhanced reactivity toward both O-H and C-H substrates in comparison to close analogues [(L)Cu(II)(O2(•-))](+), where L contains only nitrogen donor atoms. Also, comparisons of [(L)Cu(II/I)](n+) compound reduction potentials (L = various N4 vs (DMA)N3S ligands) provide evidence that (DMA)N3S is a weaker donor to copper ion than is found for any N4 ligand-complex.
authors.affiliation: Department of Chemistry, Johns Hopkins University , Baltimore, Maryland 21218, United States.
authors.forename: Sunghee
authors.initials: S
authors.lastname: Kim
authors.forename: Jung Yoon
authors.initials: JY
authors.lastname: Lee
authors.forename: Ryan E
authors.initials: RE
authors.lastname: Cowley
authors.forename: Jake W
authors.initials: JW
authors.lastname: Ginsbach
authors.forename: Maxime A
authors.initials: MA
authors.lastname: Siegler
authors.forename: Edward I
authors.initials: EI
authors.lastname: Solomon
authors.forename: Kenneth D
authors.initials: KD
authors.lastname: Karlin
mesh_terms: D003300:Copper / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D013440:Sulfides / Q000737:chemistry*
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D013440:Sulfides; D003300:Copper; D010100:Oxygen