Thiol-copper(I) and disulfide-dicopper(I) complex O(2)-reactivity leading to sulfonate-copper(II) complex or the formation of a cross-linked thioether-phenol product with phenol addition.

Thiol-copper(I) and disulfide-dicopper(I) complex O(2)-reactivity leading to sulfonate-copper(II) complex or the formation of a cross-linked thioether-phenol product with phenol addition. Research Abstract Details 

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Thiol-copper(I) and disulfide-dicopper(I) complex O(2)-reactivity leading to sulfonate-copper(II) complex or the formation of a cross-linked thioether-phenol product with phenol addition. Abstract Text:

Yunho Lee,Dong-Heon Lee,Amy A Narducci Sarjeant,Kenneth D Karlin,Yunho Lee,Dong-Heon Lee,Amy A Narducci Sarjeant,Kenneth D Karlin,Yunho Lee,Dong-Heon Lee,Amy A Narducci Sarjeant,Kenneth D Karlin,

In order to better understand copper mediated oxidative chemistry via ligand-Cu(I)/O(2) reactivity employing S-donor ligands for copper, O(2)-reactivity studies of the copper(I) complexes (1 and 2, Chart 2) have been carried out with a tridentate N(2)S thiol ligand (1-(N-methyl-N-(2-(pyridin-2-yl)ethyl)amino)propane-2-thiol; L(SH)) or its oxidized disulfide form (L(SS)). Reactions of [L(SH)Cu(I)](+) (1) and [L(SS)(Cu(I))(2)(X)(2)](2+) (2) with O(2) give approximately 90% and approximately 70% yields of [L(SO3)Cu(II)(MeOH)(2)](+) (3), respectively, where L(SO3) is S-oxygenated sulfonate; 3 was characterized by electrospray ionization (ESI) mass spectrometry and X-ray crystallography. Mimicking TyrCys galactose oxidase cofactor biogenesis, a new C-S bond is formed (within new thioether moiety L(SPhOH)) from cuprous complex (both 1 and 2) dioxygen reactivity in the presence of 2,4-tBu(2)-phenolate. In addition, the disulfide ligand (L(SS)) reacts with 2equiv. cupric ion salts and the phenolate to efficiently give the cross-linked product L(SPhOH) in high yield (>90%) under anaerobic conditions. Separately, complex [L(SPhO)Cu(II)(ClO(4))] (4), possessing the cross-linked L(SPhOH), was characterized by ESI mass spectrometry and X-ray crystallography.

Thiol-copper(I) and disulfide-dicopper(I) complex O(2)-reactivity leading to sulfonate-copper(II) complex or the formation of a cross-linked thioether-phenol product with phenol addition. Publishing Authors By Initials

Y Lee,DH Lee,AA Sarjeant,KD Karlin,Y Lee,DH Lee,AA Sarjeant,KD Karlin,Y Lee,DH Lee,AA Sarjeant,KD Karlin,

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Thiol-copper(I) and disulfide-dicopper(I) complex O(2)-reactivity leading to sulfonate-copper(II) complex or the formation of a cross-linked thioether-phenol product with phenol addition. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Journal of inorganic biochemistry

VOLUME: 101

Page Numbers: 1845-58

Journal Abbreviation: J. Inorg. Biochem.

ISSN: 0162-0134

DAY: 16

MONTH: 06

YEAR: 2007

Thiol-copper(I) and disulfide-dicopper(I) complex O(2)-reactivity leading to sulfonate-copper(II) complex or the formation of a cross-linked thioether-phenol product with phenol addition. Information

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LANGUAGE: eng

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AFFILIATION: Department of Chemistry, The Johns Hopkins University, 3400 North Charles Street, Baltimore, MD 21218, United States.

Country: United States

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MEDLINETA: J Inorg Biochem

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