Models of Lysine-Cysteine Hydrogen Bonding in Metallothionein: Hydrogen Bonding between Ammonium and Benzenethiolate in [(C6H11)2NH2]2[Co(SC6H5)4]

Wesley P. Chung, John C. Dewan, M. Anton Walters

Research output: Contribution to journalArticlepeer-review

Abstract

Anion-cation hydrogen bonding interactions are described for [(C6H11)2NH2]2[M(SC6H5)4] where M = Co (1), Zn (3), which serve as models of putative lysine-cyteine hydrogen bonding at the metal binding site of metallothionein. Complex 1 is isolated as green crystals in which an average N–H⋯S hydrogen bond length of 3.29 (1) Å is observed in infinite one-dimensional chains. The dicyclohexylammonium counterion occupies a bridging position by hydrogen bonding to thiolate ligand sulfur atoms on adjacent anion complexes. There are two [Co(SC6H5)4]2− anions per asymmetric unit where each Co atom is tetrahedrally coordinated by four benzenethiolate ligands [Co-Sav = 2.308 (4) Å]. In the non-hydrogen bonding complex [(CH3)4N)2[Co(SC6H5)4] (5), a split vibrational band at 228 cm−1 (av) is assigned to a Co-S T2 related mode. In [(CH3)4N]2[Zn(SC6H5)4] (7) this band is replaced by one at 199 cm−1. Relatively intense bands at 192 and 180 cm−1 in the Raman spectra of 1 and 3 are assigned to metal-ligand modes. Hydrogen bonding causes a decrease in metal-ligand bond length of 0.02 Å relative to the bonds in a non-hydrogen bonding complex.

Original languageEnglish (US)
Pages (from-to)525-530
Number of pages6
JournalJournal of the American Chemical Society
Volume113
Issue number2
DOIs
StatePublished - Jan 1 1991

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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