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

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

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

Lanying Q Hatcher,Dong-Heon Lee,Michael A Vance,Ashley E Milligan,Ritimukta Sarangi,Keith O Hodgson,Britt Hedman,Edward I Solomon,Kenneth D Karlin,

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}.

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

LQ Hatcher,DH Lee,MA Vance,AE Milligan,R Sarangi,KO Hodgson,B Hedman,EI Solomon,KD Karlin,

For similar environment and public health: environment: environment, controlled: temperature research abstracts see: environment and public health: environment: environment, controlled: temperature research

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

PUBLICATION TYPE: Research Support, U.S. Gov't,

Journal: Inorganic chemistry

VOLUME: 45

Page Numbers: 10055-7

Journal Abbreviation:

ISSN: 0020-1669

DAY: 11

MONTH: Dec

YEAR: 2006

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

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LANGUAGE: eng

NlmUniqueID: 366543

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

KEYWORDS: Temperature

MESH TERMS: chemistry

Chemical & Substance for Abstract: Dioxygen reactivity of a copper(I) complex with a N3S thioether chelate; peroxo-dicopper(II) formation including sulfur-ligation. Information

Substance Name: Oxygen

Registry Number: 7782-44-7

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

AFFILIATION: Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21212, USA.

Country: United States

AGENCY: United States NIGMS

GRANT: GM28962

ACRONYM: GM

MEDLINETA: Inorg Chem

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