title: Zinc, cadmium, and mercury 1,2-benzenedithiolates with intramolecular NH...S hydrogen bonds.
abstract: Mononuclear Zn, Cd, and Hg 1,2-benzenedithiolates with intramolecular NH...S hydrogen bonds, [M(II){1,2-S2-3,6-(RCONH)2C6H2}2](2-) (R = CH 3, t-Bu; M = Zn, Cd, Hg), were synthesized and characterized by X-ray analysis and spectral measurements. The presence of intramolecular NH...S hydrogen bonds was established by the IR spectra. (199)Hg and (113)Cd nuclear magnetic resonance showed a stabilized four-thiolate coordinated structure and suggested the influence of the NH...S hydrogen bonds to ppi(Hg)-ppi(S) interactions. The NH stretching bands show that the NH...S hydrogen bonds in Cd and Hg complexes are stronger than those in the corresponding Zn complex. These results are supported by theoretical calculations. The experimental and theoretical results suggested that the NH...S hydrogen bond influences the efficient capture of toxic Cd and Hg ions by metallothioneins.
authors.affiliation: Chemical Analysis Research Center, National Institute for Agro-Environmental Sciences, Tsukuba, Ibaraki 305-8604, Japan.
authors.forename: Koji
authors.initials: K
authors.lastname: Baba
authors.forename: Taka-aki
authors.initials: TA
authors.lastname: Okamura
authors.forename: Hitoshi
authors.initials: H
authors.lastname: Yamamoto
authors.forename: Tetsuo
authors.initials: T
authors.lastname: Yamamoto
authors.forename: Norikazu
authors.initials: N
authors.lastname: Ueyama
mesh_terms: D019187:Cadmium Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy; D017669:Mercury Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D013055:Spectrophotometry, Infrared; D013438:Sulfhydryl Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*; D017967:Zinc Compounds / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D019187:Cadmium Compounds; D017669:Mercury Compounds; D013438:Sulfhydryl Compounds; D017967:Zinc Compounds; C102217:1,2-benzenedithiol; D013455:Sulfur