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Dioxygen reactivity of a copper(I) complex with a N3S thioether chelate; peroxo-dicopper(II) formation including sulfur-ligation.

Authors :
Hatcher LQ
Lee DH
Vance MA
Milligan AE
Sarangi R
Hodgson KO
Hedman B
Solomon EI
Karlin KD
Source :
Inorganic chemistry [Inorg Chem] 2006 Dec 11; Vol. 45 (25), pp. 10055-7.
Publication Year :
2006

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}.

Details

Language :
English
ISSN :
0020-1669
Volume :
45
Issue :
25
Database :
MEDLINE
Journal :
Inorganic chemistry
Publication Type :
Academic Journal
Accession number :
17140210
Full Text :
https://doi.org/10.1021/ic061813c