Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Suzhou University, Suzhou 215123, People's Republic of China.
Inorg Chem. 2009 Mar 16;48(6):2639-51. doi: 10.1021/ic8021744.
Reactions of Hg(Tab)(2)(2) (1) with phen, 2,2'-bipy, py, N-Meim, N-(i)Prim, en, eten, tmen, dap, and dpt gave rise to a family of cationic mercury(II) thiolate complexes, Hg(Tab)(2)(L)(2).S (2, L = phen, S = 2MeOH; 3, L = 2,2'-bipy, S = DMF), Hg(Tab)(2)(L)(2)(2) (4, L = py; 5, L = N-Meim), Hg(Tab)(2)(N-(i)Prim)(2) (6), Hg(Tab)(2)(L)(2).0.5MeCN (7, L = en; 8, L = eten), and Hg(Tab)(2)(L)(2) (9, L = tmen; 10, L = dap; 11, L = dpt). These complexes were characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H NMR, and single-crystal X-ray crystallography. The Hg atom in Hg(Tab)(2) dications of 2-5 is further coordinated either by two N atoms from one phen or 2,2'-bipy ligand or by two N atoms from two py or N-Meim ligands, affording a distorted seesaw-shaped coordination geometry. In 6, the Hg atom of the Hg(Tab)(2) dication is coordinated by one N atom of the N-(i)Prim ligand, forming a T-shaped coordination geometry, and these Hg(Tab)(2)(N-(i)Prim) dications are further coordinated to another S atom of Tab from the adjacent unit, giving a chain structure. The Hg atoms in Hg(Tab)(2) dications of 7-11 are chelated by two N atoms from one diamine molecule such as en in 7, eten in 8, tmen in 9, or dap in 10 or by two N atoms from the triamine molecule dpt in 11, forming a distorted seesaw-shaped coordination geometry. In all of these structures, the original trans configuration of the Hg(Tab)(2) dication of 1 is changed via rotation and/or switching of the two Tab species along the S-Hg-S line together with the rotation of the phenyl groups of the Tab ligands. The results may provide interesting insight into mimicking of the interactions of the Hg(Cys)(2) linear species in Hg-MerR and Hg-MT with various N-donor ligands encountered in nature and its potential changes in the structural chemistry (bond length, angles, configurations, etc.).
Hg(Tab)(2)(2)（1）与 phen、2,2'-bipy、py、N-Meim、N-(i)Prim、en、etn、tmen、dap 和 dpt 反应生成了一系列阳离子汞(II)硫醇配合物，Hg(Tab)(2)(L)(2).S（2，L = phen，S = 2MeOH；3，L = 2,2'-bipy，S = DMF），Hg(Tab)(2)(L)(2)(2)（4，L = py；5，L = N-Meim），Hg(Tab)(2)(N-(i)Prim)(2)（6），Hg(Tab)(2)(L)(2).0.5MeCN（7，L = en；8，L = eten），和Hg(Tab)(2)(L)(2)（9，L = tmen；10，L = dap；11，L = dpt）。这些配合物通过元素分析、红外光谱、紫外可见光谱、（1）H NMR 和单晶 X 射线晶体学进行了表征。2-5 中Hg(Tab)(2)二阳离子中的 Hg 原子进一步由一个 phen 或 2,2'-bipy 配体中的两个 N 原子或两个 py 或 N-Meim 配体中的两个 N 原子配位，形成扭曲的跷跷板形配位几何形状。在 6 中，Hg(Tab)(2)二阳离子中的 Hg 原子由 N-(i)Prim 配体的一个 N 原子配位，形成 T 形配位几何形状，这些Hg(Tab)(2)(N-(i)Prim)二阳离子进一步与相邻单元中来自 Tab 的另一个 S 原子配位，形成链状结构。7-11 中Hg(Tab)(2)二阳离子中的 Hg 原子由一个二胺分子中的两个 N 原子螯合，例如 7 中的 en、8 中的 eten、9 中的 tmen 或 10 中的 dap，或由三胺分子 dpt 中的两个 N 原子螯合，形成扭曲的跷跷板形配位几何形状。在所有这些结构中，1 中Hg(Tab)(2)二阳离子的原始 trans 构型通过两个 Tab 物种沿着 S-Hg-S 线的旋转和/或切换以及 Tab 配体的苯基的旋转而改变。这些结果可能为模拟 Hg(Cys)(2)线性物种在 Hg-MerR 和 Hg-MT 中与自然界中遇到的各种 N-供体配体的相互作用及其结构化学（键长、角度、构型等）中的潜在变化提供有趣的见解。
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