Dioxygen reactivity of a copper(I) complex with a N3S thioether chelate; peroxo-dicopper(II) formation including sulfur-ligation
| Autor: | Keith O. Hodgson, Michael A. Vance, Ritimukta Sarangi, Kenneth D. Karlin, Edward I. Solomon, Lanying Q. Hatcher, Britt Hedman, Dong-Heon Lee, Ashley E. Milligan |
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| Rok vydání: | 2006 |
| Předmět: |
Absorption spectroscopy
Pyridines Resonance Raman spectroscopy chemistry.chemical_element Sulfides Photochemistry Ligands Adduct Inorganic Chemistry Acetone chemistry.chemical_compound Thioether Reactivity (chemistry) Physical and Theoretical Chemistry Furans Chelating Agents Methylene Chloride Chemistry Ligand Spectrum Analysis Temperature Copper Peroxides Oxygen Crystallography Amine gas treating Sulfur |
| Zdroj: | Inorganic chemistry. 45(25) |
| ISSN: | 0020-1669 |
| Popis: | 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}. |
| Databáze: | OpenAIRE |
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