title: Dioxygen reactivity of a copper(I) complex with a N3S thioether chelate; peroxo-dicopper(II) formation including sulfur-ligation.
abstract: Employing a tetradentate N3S(thioether) ligand, LN3S, dioxygen reactivity of a copper(I) complex, [(LN3S)CuI]+ (1) was examined. In CH2Cl2, acetone (at -80 degrees C), or 2-methyltetrahydrofuran (at -128 degrees C), 1 reacts with O2 producing the end-on bound peroxodicopper(II) complex [{(LN3S)CuII}2(mu-1,2-O2(2-))]2+ (2), the first reported copper-dioxygen adduct with sulfur (thioether) ligation. Its absorption spectrum contains an additional low-energy feature (but not a Cu-S CT band) compared to the previously well-characterized N4 ligand complex, [{(TMPA)CuII}2(mu-1,2-O2(2-))]2+ (3) (TMPA = tris(2-pyridylmethyl)amine). Resonance Raman spectroscopy confirms the peroxo formulation {nu(O-O) = 817 cm-1 (16-18O2 Delta = 46 cm-1) and nu(Cu-O) = 545 cm-1 (16-18O2 Delta = 26 cm-1), in close analogy to that known for 3 {nu(O-O) = 827 cm-1 and nu(Cu-O) = 561 cm-1}. Direct evidence for thioether ligation comes from EXAFS spectroscopy {Cu K-edge; Cu-S = 2.4 A}.
authors.affiliation: Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21212, USA.
authors.forename: Lanying Q
authors.initials: LQ
authors.lastname: Hatcher
authors.forename: Dong-Heon
authors.initials: DH
authors.lastname: Lee
authors.forename: Michael A
authors.initials: MA
authors.lastname: Vance
authors.forename: Ashley E
authors.initials: AE
authors.lastname: Milligan
authors.forename: Ritimukta
authors.initials: R
authors.lastname: Sarangi
authors.forename: Keith O
authors.initials: KO
authors.lastname: Hodgson
authors.forename: Britt
authors.initials: B
authors.lastname: Hedman
authors.forename: Edward I
authors.initials: EI
authors.lastname: Solomon
authors.forename: Kenneth D
authors.initials: KD
authors.lastname: Karlin
mesh_terms: D000096:Acetone / Q000737:chemistry; D002614:Chelating Agents / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D005663:Furans / Q000737:chemistry; D008024:Ligands; D008752:Methylene Chloride / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry*; D010545:Peroxides / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry; D013057:Spectrum Analysis; D013440:Sulfides / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*; D013696:Temperature
chemical_list: D002614:Chelating Agents; D005663:Furans; D008024:Ligands; D010545:Peroxides; D011725:Pyridines; D013440:Sulfides; C431843:tris(2-pyridylmethyl)amine; D000096:Acetone; C018674:tetrahydrofuran; D008752:Methylene Chloride; D013455:Sulfur; D003300:Copper; D010100:Oxygen