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Organomercury Compounds Containing Three-Coordinate Mercury. Synthesis and Spectroscopic Studies of Cationic Complexes of Methylmercury(II) with Neutral Donor Ligands

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Canty, AJ and Marker, A (1976) Organomercury Compounds Containing Three-Coordinate Mercury. Synthesis and Spectroscopic Studies of Cationic Complexes of Methylmercury(II) with Neutral Donor Ligands. Inorganic Chemistry, 15 (2). pp. 425-430. ISSN 0020-1669

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Abstract

Synthetic and spectroscopic studies of cationic complexes of methylmercury(II), [MeHgL][N03], are reported. The complexes [MeHgL][NO3] (L = pyridine; 2-methyl-, 3-methyl-, 4-methyl-, 2-benzyl-, 2,4-dimethyl-, and 2,6-dimethylpyridine; 2,2'-bipyridyl; 3,3'-dimethyl-, 4,4'-dimethyl-, 5,5'-dimethyl-, and 6,6'-dimethyl-2,2'-bipyridyl;, l0-phenanthroline; 2,9-dimethyl-,
4,7-dimethyl-, and 5,6-dimethyl-1,10-phenanthroline) are obtained from addition reactions in acetone. A complex of composition MeHgN03.1/2L is also formed by 3,3'-dimethyl-2,2'-bipyridyl. Infrared evidence for coordination of ligands in the solid complexes is presented. Proton magnetic resonance spectra indicate that the complexes of 2,2'-bipyridyls (except for those of 3,3'-dimethyl-2,2'-bipyridyl) and 1,10-phenanthrolines have three-coordinate mercury in solution. A linear correlation is observed between J(1H-199Hg) and protonation constants of the ligands, with separate relationships for complexes of
unidentate ligands, bidentate 2,2'-bipyridyls, and 1,l0-phenanthrolines. Aspects of bonding in three-coordinate complexes are deduced from 1H and 13C NMR of the complexes and an X-ray structural determination of [MeHg(2,2'-bpy)][N03]. Bonding between mercury and carbon in the three-coordinate complexes is considered to be similar to that in the linear sp-hybridized complexes of pyridine ligands. Comparison of structural data for the 2,2'-bipyridyl and some amino acid complexes of methylmercury suggests that a similar sp hybridization bonding model is applicable for the latter complexes.

Item Type: Article
Journal or Publication Title: Inorganic Chemistry
Page Range: pp. 425-430
ISSN: 0020-1669
Identification Number - DOI: 10.1021/ic50156a037
Date Deposited: 18 Jan 2008 00:59
Last Modified: 18 Nov 2014 03:27
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