Reactions of a methylmercury zwitterionic thiolate complex [MeHg(Tab)]PF6 with various donor ligands: relevance to methylmercury detoxification.
Reactions of a methylmercury zwitterionic thiolate complex [MeHg(Tab)]PF6 with various donor ligands: relevance to methylmercury detoxification.
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DOI：
10.1039/c2dt12219g
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发表时间：
2012-03
影响因子：
4
通讯作者：
Ai-Xia Zheng;Hong‐Xi Li;Kai-Peng Hou;Jingwen Shi;Hui-Fang Wang;Zhi‐Gang Ren;J. Lang
中科院分区：
文献类型：
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作者：
Ai-Xia Zheng;Hong‐Xi Li;Kai-Peng Hou;Jingwen Shi;Hui-Fang Wang;Zhi‐Gang Ren;J. Lang
MeHgI 与 Ag(2)O 在 H(2)O 中反应，然后添加等摩尔的 TabHPF(6) 在 MeCN 中，以高产率生成甲基汞两性离子硫醇络合物 [MeHg(Tab)]PF(6) (1) (TabH = 4-(三甲基氨基)苯硫醇)。用 KI 和 KSCN 处理 1 分别得到阴离子交换产物 [MeHg(Tab)]I·0.25H(2)O (2·0.25H(2)O) 和 [MeHg(Tab)]SCN (3)，而用等摩尔 Tab 处理 1 则导致形成另一种 MeHg/Tab 化合物 [MeHg(Tab)(2)]PF(6) (4)。 2或3的阳离子显示近似线性结构，其中中心Hg(II)由1个CH(3)基团的1个C原子和Tab配体的1个S原子配位。 4的阳离子的Hg(ii)中心由CH(3)基团的一个C原子和两个Tab配体的两个S原子进行三角配位。 1 与 NH(4)SCN 的类似反应导致 1 的 Hg-C 键断裂并形成已知的四配位 Hg(II)/Tab 络合物 [Hg(Tab)(2)(SCN)(2)] (5)。当4用4,6-Me(2)pymSH或EtSH处理时，以高产率生成另一种四配位Hg(II)/Tab络合物[Hg(Tab)(4)](3)(PF(6))(6) (6)。 6 的每个阳离子的 Hg(II) 中心由四个 Tab 配体的四个 S 原子进行四面体配位。结果表明，甲基汞配合物1中Hg-C键的断裂可以通过S-供体配体增加其Hg(II)中心的配位数并通过弱酸质子化甲基来完成。
Reaction of MeHgI with Ag(2)O in H(2)O followed by addition of equimolar TabHPF(6) in MeCN gave rise to a methylmercury zwitterionic thiolate complex [MeHg(Tab)]PF(6) (1) (TabH = 4-(trimethylammonio)benzenethiol) in a high yield. Treatment of 1 with KI and KSCN afforded an anion exchange product [MeHg(Tab)]I·0.25H(2)O (2·0.25H(2)O) and [MeHg(Tab)]SCN (3), respectively, while that of 1 with equimolar Tab resulted in the formation of another MeHg/Tab compound [MeHg(Tab)(2)]PF(6) (4). The cation of 2 or 3 shows an approximately linear structure in which the central Hg(II) is coordinated by one C atom of one CH(3) group and one S atom of a Tab ligand. The Hg(ii) center of the cation of 4 is trigonally coordinated by one C atom of the CH(3) group and two S atoms of two Tab ligands. The analogous reaction of 1 with NH(4)SCN led to the cleavage of the Hg-C bond of 1 and the formation of a known four-coordinated Hg(II)/Tab complex [Hg(Tab)(2)(SCN)(2)] (5). When 4 was treated with 4,6-Me(2)pymSH or EtSH, another four-coordinated Hg(II)/Tab complex [Hg(Tab)(4)](3)(PF(6))(6) (6) was generated in a high yield. The Hg(II) center of each cation of 6 is tetrahedrally coordinated by four S atoms of four Tab ligands. The results suggested that cleavage of the Hg-C bond in the methylmercury complex 1 could be completed by increasing the coordination number of its Hg(II) center by S-donor ligands and protonating the methyl group by weak acids.