The ligand unwrapping/rewrapping pathway that exchanges metals in S-acetylated, hexacoordinate N2S2O2 complexes

J. A. Denny, W. S. Foley, A. D. Todd, M. Y. Darensbourg

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2 Scopus citations

Abstract

The effect of S-acetylation in MN2S2 complexes on metal exchange reactivity was examined in a series of MN2S2O2 complexes. While clean exchange processes do not occur for the MN2S2 derivatives where formation of S-bridged aggregates predominate, acetylation permits the metal exchange with hierarchy that follows the Irving-Williams series of stability for first row transition metals: Fe2+ < Co2+ < Ni2+ < Cu2+ > Zn2+. The rate determining step consistent with kinetic parameters depends on both M and M′, supporting a mechanism of exchange that involves ligand unwrapping/rewrapping process as earlier defined by Margerum et al. for M(EDTA) systems. The enhanced metal exchange deriving from S-acetylation is of significance to probes and detection of cysteine-S metallo-proteins and metallo-enzyme active sites, and highlights a new role for S-acetylation.

Original languageEnglish (US)
Pages (from-to)7079-7088
Number of pages10
JournalChemical Science
Volume6
Issue number12
DOIs
StatePublished - Sep 7 2015

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© The Royal Society of Chemistry.

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