Zinc, cadmium, and mercury 1,2-benzenedithiolates with intramolecular NH•••S hydrogen bonds
Zinc, cadmium, and mercury 1,2-benzenedithiolates with intramolecular NH•••S hydrogen bonds
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DOI：
10.1021/ic702037k
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发表时间：
2008-04-07
影响因子：
4.6
通讯作者：
Ueyama, Norikazu
中科院分区：
文献类型：
--
作者：
Baba, Koji;Okamura, Taka-Aki;Ueyama, Norikazu
合成了具有分子内 NH 中心点中心点中心点 S 氢键的单核 Zn、Cd 和 Hg 1,2-苯二硫醇盐，[M-II{1,2-S-2-3,6-(RCONH)(2)C6H2}(2)](2-) (R = CH3, t-Bu; M = Zn, Cd, Hg)，并通过 X 射线分析进行表征 和光谱测量。通过红外光谱确定分子内 NH 中心点 S 氢键的存在。 Hg-199和Cd-113核磁共振显示出稳定的四硫醇配位结构，并表明NH中心点中心点中心点S氢键对p pi(Hg)-p pi(S)相互作用的影响。 NH伸缩带表明Cd和Hg配合物中的NH中心点中心点中心点S氢键比相应的Zn配合物中的氢键更强。这些结果得到了理论和计算的支持。实验和理论结果表明NH中心点S氢键影响金属硫蛋白对有毒Cd和Hg离子的有效捕获。
Mononuclear Zn, Cd, and Hg 1,2-benzenedithiolates with intramolecular NH center dot center dot center dot S hydrogen bonds, [M-II{1,2-S-2-3,6-(RCONH)(2)C6H2}(2)](2-) (R = CH3, t-Bu; M = Zn, Cd, Hg), were synthesized and characterized by X-ray analysis and spectral measurements. The presence of intramolecular NH center dot center dot center dot S hydrogen bonds was established by the IR spectra. Hg-199 and Cd-113 nuclear magnetic resonance showed a stabilized four-thiolate coordinated structure and suggested the influence of the NH center dot center dot center dot S hydrogen bonds to p pi(Hg)-p pi(S) interactions. The NH stretching bands show that the NH center dot center dot center dot 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 center dot center dot center dot S hydrogen bond influences the efficient capture of toxic Cd and Hg ions by metallothioneins.