Baba Koji, Okamura Taka-aki, Yamamoto Hitoshi, Yamamoto Tetsuo, Ueyama Norikazu
Chemical Analysis Research Center, National Institute for Agro-Environmental Sciences, Tsukuba, Ibaraki 305-8604, Japan.
Inorg Chem. 2008 Apr 7;47(7):2837-48. doi: 10.1021/ic702037k. Epub 2008 Mar 11.
Mononuclear Zn, Cd, and Hg 1,2-benzenedithiolates with intramolecular NH...S hydrogen bonds, M(II){1,2-S2-3,6-(RCONH)2C6H2}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.
具有分子内NH…S氢键的单核锌、镉和汞的1,2-苯二硫醇盐，M(II){1,2-S2-3,6-(RCONH)2C6H2}2（R = CH3，t-Bu；M = Zn，Cd，Hg），通过X射线分析和光谱测量进行了合成和表征。红外光谱确定了分子内NH…S氢键的存在。(199)Hg和(113)Cd核磁共振显示出稳定的四硫醇盐配位结构，并表明了NH…S氢键对ppi(Hg)-ppi(S)相互作用的影响。NH伸缩带表明，镉和汞配合物中的NH…S氢键比相应锌配合物中的更强。这些结果得到了理论计算的支持。实验和理论结果表明，NH…S氢键影响金属硫蛋白对有毒镉和汞离子的有效捕获。
