Solid-state and solution-state coordination chemistry of the zinc triad with the mixed N,S donor ligand bis(2-methylpyridyl) sulfide

Steven M. Berry; Deborah C. Bebout; Raymond J. Butcher

doi:10.1021/ic048915s

Solid-state and solution-state coordination chemistry of the zinc triad with the mixed N,S donor ligand bis(2-methylpyridyl) sulfide

Steven M. Berry, Deborah C. Bebout, Raymond J. Butcher

Chemistry & Biochemistry

Research output: Contribution to journal › Article › peer-review

56 Scopus citations

Abstract

The binding of group 12 metal ions to bis(2-methylpyridyl) sulfide (1) was investigated by X-ray crystallography and NMR. Seven structures of the chloride and perchlorate salts of Hg(II), Cd(II), and Zn(II) with 1 are reported. Hg-(1)₂(ClO₄)₂, Cd(1)₂(ClO ₄)₂, and Zn(1)₂(ClO₄) ₂·CH₃CN form mononuclear, six-coordinate species in the solid state with 1 binding in a tridentate coordination mode. Hg(1) ₂(ClO₄)₂ has a distorted trigonal prismatic coordination geometry while Cd(1)₂(ClO₄)₂ and Zn(1)₂(ClO₄)₂·CH₃CN have distorted octahedral geometries. With chloride anions, the 1:1 metal to ligand complexes Hg(1)Cl₂, [Cd(1)Cl₂]₂, and Zn(1)Cl₂ are formed. A bidentate binding mode that lacks thioether coordination is observed for 1 in the four-coordinate, distorted tetrahedral complexes Zn(1)Cl₂ and Hg-(1)Cl₂. [Cd(1)Cl ₂]₂ is dimeric with a distorted octahedral coordination geometry and a tridentate 1. Hg(1)Cl₂ is comprised of pairs of loosely associated monomers and Zn(1)Cl₂ is monomeric. In addition, Hg₂(1)Cl₄ is formed with alternating chloride and thioether bridges. The distorted square pyramidal Hg(II) centers result in a supramolecular zigzagging chain in the solid state. The solution ¹H NMR spectra of [Hg(1)₂]²⁺ and [Hg(1)(NCCH ₃)_x]²⁺ reveal ^3-5J( ¹⁹⁹Hg¹H) due to slow ligand exchange found in these thioether complexes. Implications for use of Hg(II) as a metallobioprobe are discussed.

Original language	English (US)
Pages (from-to)	27-39
Number of pages	13
Journal	Inorganic chemistry
Volume	44
Issue number	1
DOIs	https://doi.org/10.1021/ic048915s
State	Published - Jan 10 2005

Access

10.1021/ic048915s

OpenUrl availability

Full text

Cite this

@article{6f5ac852082b419db611956f08f5a131,

title = "Solid-state and solution-state coordination chemistry of the zinc triad with the mixed N,S donor ligand bis(2-methylpyridyl) sulfide",

abstract = "The binding of group 12 metal ions to bis(2-methylpyridyl) sulfide (1) was investigated by X-ray crystallography and NMR. Seven structures of the chloride and perchlorate salts of Hg(II), Cd(II), and Zn(II) with 1 are reported. Hg-(1)2(ClO4)2, Cd(1)2(ClO 4)2, and Zn(1)2(ClO4) 2·CH3CN form mononuclear, six-coordinate species in the solid state with 1 binding in a tridentate coordination mode. Hg(1) 2(ClO4)2 has a distorted trigonal prismatic coordination geometry while Cd(1)2(ClO4)2 and Zn(1)2(ClO4)2·CH3CN have distorted octahedral geometries. With chloride anions, the 1:1 metal to ligand complexes Hg(1)Cl2, [Cd(1)Cl2]2, and Zn(1)Cl2 are formed. A bidentate binding mode that lacks thioether coordination is observed for 1 in the four-coordinate, distorted tetrahedral complexes Zn(1)Cl2 and Hg-(1)Cl2. [Cd(1)Cl 2]2 is dimeric with a distorted octahedral coordination geometry and a tridentate 1. Hg(1)Cl2 is comprised of pairs of loosely associated monomers and Zn(1)Cl2 is monomeric. In addition, Hg2(1)Cl4 is formed with alternating chloride and thioether bridges. The distorted square pyramidal Hg(II) centers result in a supramolecular zigzagging chain in the solid state. The solution 1H NMR spectra of [Hg(1)2]2+ and [Hg(1)(NCCH 3)x]2+ reveal 3-5J( 199Hg1H) due to slow ligand exchange found in these thioether complexes. Implications for use of Hg(II) as a metallobioprobe are discussed.",

author = "Berry, {Steven M.} and Bebout, {Deborah C.} and Butcher, {Raymond J.}",

year = "2005",

month = jan,

day = "10",

doi = "10.1021/ic048915s",

language = "English (US)",

volume = "44",

pages = "27--39",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "1",

}

TY - JOUR

T1 - Solid-state and solution-state coordination chemistry of the zinc triad with the mixed N,S donor ligand bis(2-methylpyridyl) sulfide

AU - Berry, Steven M.

AU - Bebout, Deborah C.

AU - Butcher, Raymond J.

PY - 2005/1/10

Y1 - 2005/1/10

N2 - The binding of group 12 metal ions to bis(2-methylpyridyl) sulfide (1) was investigated by X-ray crystallography and NMR. Seven structures of the chloride and perchlorate salts of Hg(II), Cd(II), and Zn(II) with 1 are reported. Hg-(1)2(ClO4)2, Cd(1)2(ClO 4)2, and Zn(1)2(ClO4) 2·CH3CN form mononuclear, six-coordinate species in the solid state with 1 binding in a tridentate coordination mode. Hg(1) 2(ClO4)2 has a distorted trigonal prismatic coordination geometry while Cd(1)2(ClO4)2 and Zn(1)2(ClO4)2·CH3CN have distorted octahedral geometries. With chloride anions, the 1:1 metal to ligand complexes Hg(1)Cl2, [Cd(1)Cl2]2, and Zn(1)Cl2 are formed. A bidentate binding mode that lacks thioether coordination is observed for 1 in the four-coordinate, distorted tetrahedral complexes Zn(1)Cl2 and Hg-(1)Cl2. [Cd(1)Cl 2]2 is dimeric with a distorted octahedral coordination geometry and a tridentate 1. Hg(1)Cl2 is comprised of pairs of loosely associated monomers and Zn(1)Cl2 is monomeric. In addition, Hg2(1)Cl4 is formed with alternating chloride and thioether bridges. The distorted square pyramidal Hg(II) centers result in a supramolecular zigzagging chain in the solid state. The solution 1H NMR spectra of [Hg(1)2]2+ and [Hg(1)(NCCH 3)x]2+ reveal 3-5J( 199Hg1H) due to slow ligand exchange found in these thioether complexes. Implications for use of Hg(II) as a metallobioprobe are discussed.

AB - The binding of group 12 metal ions to bis(2-methylpyridyl) sulfide (1) was investigated by X-ray crystallography and NMR. Seven structures of the chloride and perchlorate salts of Hg(II), Cd(II), and Zn(II) with 1 are reported. Hg-(1)2(ClO4)2, Cd(1)2(ClO 4)2, and Zn(1)2(ClO4) 2·CH3CN form mononuclear, six-coordinate species in the solid state with 1 binding in a tridentate coordination mode. Hg(1) 2(ClO4)2 has a distorted trigonal prismatic coordination geometry while Cd(1)2(ClO4)2 and Zn(1)2(ClO4)2·CH3CN have distorted octahedral geometries. With chloride anions, the 1:1 metal to ligand complexes Hg(1)Cl2, [Cd(1)Cl2]2, and Zn(1)Cl2 are formed. A bidentate binding mode that lacks thioether coordination is observed for 1 in the four-coordinate, distorted tetrahedral complexes Zn(1)Cl2 and Hg-(1)Cl2. [Cd(1)Cl 2]2 is dimeric with a distorted octahedral coordination geometry and a tridentate 1. Hg(1)Cl2 is comprised of pairs of loosely associated monomers and Zn(1)Cl2 is monomeric. In addition, Hg2(1)Cl4 is formed with alternating chloride and thioether bridges. The distorted square pyramidal Hg(II) centers result in a supramolecular zigzagging chain in the solid state. The solution 1H NMR spectra of [Hg(1)2]2+ and [Hg(1)(NCCH 3)x]2+ reveal 3-5J( 199Hg1H) due to slow ligand exchange found in these thioether complexes. Implications for use of Hg(II) as a metallobioprobe are discussed.

UR - http://www.scopus.com/inward/record.url?scp=11244272817&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=11244272817&partnerID=8YFLogxK

U2 - 10.1021/ic048915s

DO - 10.1021/ic048915s

M3 - Article

C2 - 15627357

AN - SCOPUS:11244272817

SN - 0020-1669

VL - 44

SP - 27

EP - 39

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 1

ER -

Solid-state and solution-state coordination chemistry of the zinc triad with the mixed N,S donor ligand bis(2-methylpyridyl) sulfide

Abstract

Access

OpenUrl availability

Other files and links

Fingerprint

Cite this