由预制化合物[Hg(Tab)₂](PF₆)₂ [Tab = 4-(三甲基铵基)苯硫醇盐]组装新型汞(II)两性离子硫醇盐配合物家族。

Assembly of a new family of mercury(II) zwitterionic thiolate complexes from a preformed compound [Hg(Tab)2](PF6)2 [Tab = 4-(trimethylammonio)benzenethiolate].

作者信息

Chen Jin-Xiang, Zhang Wen-Hua, Tang Xiao-Yan, Ren Zhi-Gang, Zhang Yong, Lang Jian-Ping

机构信息

Key Laboratory of Organic Synthesis of Jiangsu Province, School of Chemistry and Chemical Engineering, Suzhou University, Suzhou 215123, Jiangsu, People's Republic of China.

出版信息

Inorg Chem. 2006 Mar 20;45(6):2568-80. doi: 10.1021/ic051875n.

DOI:10.1021/ic051875n

PMID:16529478

Abstract

Reactions of Hg(OAc)2 with 2 equiv of TabHPF6 [TabH = 4-(trimethylammonio)benzenethiol] in MeCN/MeOH afforded a mononuclear linear complex Hg(Tab)22 (1). By using 1 as a precursor, a new family of mercury(II) zwitterionic thiolate complexes, Hg2(Tab)64.2MeCN (2.2MeCN), Hg(Tab)2(SCN) (3), [Hg(Tab)2(SCN)2] (4), [Hg(Tab)I2] (5), {[Hg(Tab)2]4[HgI2][Hg2I6]}(PF6)2(NO3)4 (6), [Hg(Tab)2][HgI4] (7), [Hg(Tab)2][HgCl2(SCN)2] (8), [Tab-Tab]2[Hg3Cl10] (9), and [Hg2(Tab)6]3(PF6)Cl11 (10), were prepared and characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR, and single-crystal X-ray crystallography. The [Hg2(Tab)6]4+ tetracation of 2 or 10 contains an asymmetrical Hg2S2 rhomb with an inversion center lying on the midpoint of the Hg...Hg line. The Hg atom of the [Hg(Tab)2]2+ dication of 3 is coordinated to one SCN-, forming a rare T-shaped coordination geometry, while in 4, the Hg atom of [Hg(Tab)2]2+ is coordinated to two SCN-, forming a seesaw-shaped coordination geometry. Through weak secondary Hg...S coordinations, each cation in 3 is further linked to afford a one-dimensional zigzag chain. The trigonal [Hg(Tab)I2] molecules in 5 are held together by weak secondary Hg...I and Hg...S interactions, forming a one-dimensional chain structure. In 6, the four [Hg(Tab)2]2+ dications, one HgI2 molecule, one [Hg2I6]2- dianion, one PF6-, and four NO3- anions are interconnected by complicated secondary Hg...I and Hg...O interactions, forming a scolopendra-like chain structure. The secondary Hg...I interactions, [Hg(Tab)2]2+ and [HgI4]2- in 7, are combined to generate a one-dimensional chain structure, while [Hg(Tab)2]2+ and [HgCl2(SCN)2]2- in 8 are interconnected by secondary Hg...N interactions to form a one-dimensional zigzag chain structure. Compound 9 consists of two [Tab-Tab]2+ dications and one [Hg3Cl10]4- tetraanion. The facile approach to the construction of 2-8 and 10 from 1 may be applicable to the mimicking of a coordination sphere of the Hg sites of metallothioneins.

摘要

Hg(OAc)₂ 与 2 当量的 TabHPF₆ [TabH = 4-(三甲基铵基)苯硫醇] 在 MeCN/MeOH 中反应得到单核线性配合物 Hg(Tab)₂₂ (1)。以 1 为前体，制备了一系列新型汞(II)两性离子硫醇盐配合物，Hg₂(Tab)₆₄·2MeCN (2·2MeCN)、Hg(Tab)₂(SCN) (3)、[Hg(Tab)₂(SCN)₂] (4)、[Hg(Tab)I₂] (5)、{[Hg(Tab)₂]₄[HgI₂][Hg₂I₆]}(PF₆)₂(NO₃)₄ (6)、[Hg(Tab)₂][HgI₄] (7)、[Hg(Tab)₂][HgCl₂(SCN)₂] (8)、[Tab-Tab]₂[Hg₃Cl₁₀] (9) 和 [Hg₂(Tab)₆]₃(PF₆)Cl₁₁ (10)，并通过元素分析、红外光谱、紫外可见光谱、¹H NMR 和单晶 X 射线晶体学对其进行了表征。2 或 10 的 [Hg₂(Tab)₆]⁴⁺ 四核阳离子包含一个不对称的 Hg₂S₂ 菱形，其对称中心位于 Hg…Hg 线的中点。3 的 [Hg(Tab)₂]²⁺ 二价阳离子的 Hg 原子与一个 SCN⁻ 配位，形成罕见的 T 形配位几何结构，而在 4 中，[Hg(Tab)₂]²⁺ 的 Hg 原子与两个 SCN⁻ 配位，形成跷跷板形配位几何结构。通过弱的二级 Hg…S 配位，3 中的每个阳离子进一步连接形成一维锯齿链。5 中的三角 [Hg(Tab)I₂] 分子通过弱的二级 Hg…I 和 Hg…S 相互作用聚集在一起，形成一维链结构。在 6 中，四个 [Hg(Tab)₂]²⁺ 二价阳离子、一个 HgI₂ 分子、一个 [Hg₂I₆]²⁻ 二价阴离子、一个 PF₆⁻ 和四个 NO₃⁻ 阴离子通过复杂的二级 Hg…I 和 Hg…O 相互作用相互连接，形成蜈蚣状链结构。7 中的二级 Hg…I 相互作用、[Hg(Tab)₂]²⁺ 和 [HgI₄]²⁻ 结合形成一维链结构，而 8 中的 [Hg(Tab)₂]²⁺ 和 [HgCl₂(SCN)₂]²⁻ 通过二级 Hg…N 相互作用相互连接形成一维锯齿链结构。化合物 9 由两个 [Tab-Tab]²⁺ 二价阳离子和一个 [Hg₃Cl₁₀]⁴⁻ 四价阴离子组成。从 1 构建 2 - 8 和 10 的简便方法可能适用于模拟金属硫蛋白中 Hg 位点的配位环境。