Thioether sulfur oxygenation from O2 or H2O2 reactivity of copper complexes with tridentate N2Sthioether ligands.

Thioether sulfur oxygenation from O2 or H2O2 reactivity of copper complexes with tridentate N2Sthioether ligands. Research Abstract Details 

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Thioether sulfur oxygenation from O2 or H2O2 reactivity of copper complexes with tridentate N2Sthioether ligands. Abstract Text:

Yunho Lee,Dong-Heon Lee,Amy A Narducci Sarjeant,Lev N Zakharov,Arnold L Rheingold,Kenneth D Karlin,

To model thioether-copper coordination chemistry including oxidative reactivity, such as occurs in the copper monooxygenases peptidylglycine -hydroxylating monooxygenase (PHM) and dopamine beta-hydroxylase (DbetaH), we have synthesized new tridentate N2S ligands LSEP and LSBz [LSEP = methyl(2-phenethylsulfanylpropyl)(2-pyridin-2-ylethyl)amine; LSBz = (2-benzylsulfanylpropyl)methyl(2-pyridin-2-ylethyl)amine)]. Both copper(I) and copper(II) complexes have been prepared, and their respective O2 and H2O2 chemistry has been studied. Under mild conditions, oxygenation of [(LSEP)CuI]+ (1a) and [(LSBz)CuI]+ (2a) leads to ligand sulfoxidation, thus exhibiting copper monooxygenase activity. A copper(II) complex of this sulfoxide ligand product, [(LSOEP)CuII(CH3OH)(OClO3)2], has been structurally characterized, demonstrating Cu-Osulfoxide ligation. The X-ray structure of [(LSEP)CuII(H2O)(OClO3)]+ (1b) and its solution UV-visible spectral properties [S-CuII LMCT band at 365 nm (MeCN solvent); epsilon = 4285 M-1 cm-1] indicate the thioether sulfur atom is bound to the cupric ion in both the solid (CuII-S distance: 2.31 A) and solution states. Reaction of 1b with H2O2 leads to sulfonation via the sulfoxide; excess hydrogen peroxide gives mostly sulfone product. These results may provide some insight into recent reports concerning protein methionine oxidation, showing the potential importance of copper-mediated oxidation processes in certain biological settings.

Thioether sulfur oxygenation from O2 or H2O2 reactivity of copper complexes with tridentate N2Sthioether ligands. Publishing Authors By Initials

Y Lee,DH Lee,AA Sarjeant,LN Zakharov,AL Rheingold,KD Karlin,

For similar inorganic chemicals: elements: chalcogens: sulfur research abstracts see: inorganic chemicals: elements: chalcogens: sulfur research

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Thioether sulfur oxygenation from O2 or H2O2 reactivity of copper complexes with tridentate N2Sthioether ligands. Journal Published:

PUBLICATION TYPE: Research Support, Non-U.S. Gov

Journal: Inorganic chemistry

VOLUME: 45

Page Numbers: 10098-107

Journal Abbreviation:

ISSN: 0020-1669

DAY: 11

MONTH: Dec

YEAR: 2006

Thioether sulfur oxygenation from O2 or H2O2 reactivity of copper complexes with tridentate N2Sthioether ligands. Information

Number of References:

LANGUAGE: eng

NlmUniqueID: 366543

Thioether sulfur oxygenation from O2 or H2O2 reactivity of copper complexes with tridentate N2Sthioether ligands. Keywords Mesh Terms:

KEYWORDS: Sulfur

MESH TERMS: chemistry

Chemical & Substance for Abstract: Thioether sulfur oxygenation from O2 or H2O2 reactivity of copper complexes with tridentate N2Sthioether ligands. Information

Substance Name: peptidylglycine monooxygenase

Registry Number: EC 1.14.17.3

Grant and Affiliation Information for Thioether sulfur oxygenation from O2 or H2O2 reactivity of copper complexes with tridentate N2Sthioether ligands.

AFFILIATION: Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA.

Country: United States

AGENCY: United States NIGMS

GRANT: GM 28962

ACRONYM: GM

MEDLINETA: Inorg Chem

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