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

doi:10.1021/ja00002a021

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

Chemistry

Research output: Contribution to journal › Article › peer-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-S_av = 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 language	English (US)
Pages (from-to)	525-530
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	113
Issue number	2
DOIs	https://doi.org/10.1021/ja00002a021
State	Published - Jan 1 1991

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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@article{1fb078ad2fec44bf88f789955821fc62,

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

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) {\AA} 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) {\AA}]. 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 {\AA} relative to the bonds in a non-hydrogen bonding complex.",

author = "Chung, {Wesley P.} and Dewan, {John C.} and Walters, {M. Anton}",

year = "1991",

month = jan,

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doi = "10.1021/ja00002a021",

language = "English (US)",

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T1 - Models of Lysine-Cysteine Hydrogen Bonding in Metallothionein

T2 - Hydrogen Bonding between Ammonium and Benzenethiolate in [(C6H11)2NH2]2[Co(SC6H5)4]

AU - Chung, Wesley P.

AU - Dewan, John C.

AU - Walters, M. Anton

PY - 1991/1/1

Y1 - 1991/1/1

N2 - 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.

AB - 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.

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

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