Reactions of the cationic zinc thiolate model complex [Zn(Tab)4](PF6)2 with N-donor ligands and cobalt dichloride.
Reactions of the cationic zinc thiolate model complex [Zn(Tab)4](PF6)2 with N-donor ligands and cobalt dichloride.
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DOI：
10.1021/ic301191n
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发表时间：
2012-09
影响因子：
4.6
通讯作者：
Ai-Xia Zheng;Jing Si;Xiaoyan Tang;Li-Li Miao-Li;Miao-Jia Yu;Kai-Peng Hou;Fan Wang;Hong‐Xi Li;J. Lang
中科院分区：
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作者：
Ai-Xia Zheng;Jing Si;Xiaoyan Tang;Li-Li Miao-Li;Miao-Jia Yu;Kai-Peng Hou;Fan Wang;Hong‐Xi Li;J. Lang
[Zn(Tab)(4)](Pf(6))(2)(Tab=4-(三甲基氨基)苯硫酸酯)(1)与2，2‘-联吡啶(2，2’-bipy)、1，10-菲咯啉(Phen)、2，9-二甲基-1，10-菲咯啉(2，9-dmphen)、N-甲基咪唑(N-meim)和2，6-双(吡唑-3-基)吡啶(Bppy)的反应或与CoCl2·6H(2)O的反应4，4‘-二甲基-2，2’-联吡啶(4，4‘-dmbpy)，2，6-二(3，5-二甲基-1H-吡唑-1-基)吡啶(Bdmppy)得到一族锌或钴硫酸盐配合物，[Zn(Tab)(2)(L)](PF(6))(2)(2)(2：L=2，2’-bipy，3：L=phen，4：L=2，9-dmphen)，[Zn(Tab)(2)(N-Meim)(2)](PF(6))(2)(5)，[锌(Tab)(2)(Bppy)](Pf(6))(2)(6)，[Co(Tab)(2)(L)(2)](Pf(6))(3)(7：L=2，2‘-bipy，8：L=phen，9：L=4，4’-dmbpy)，以及[Co(Tab)(Bdmppy)Cl](PF(6))(10)。通过元素分析、红外光谱、紫外-可见光谱、核磁共振氢谱、电喷雾电离(ESI)和单晶X-射线衍射谱对化合物进行了表征。2-5的[Zn(Tab)(2)L(N)](2+)中的锌(II)是由两个Tab配体和一个L或两个N-Meim配体四面体配位的。在6中，锌(II)具有扭曲的三角-双锥构型，由两个Tab配体和一个三齿bppy配体配位。在7-9的[Co(Tab)(2)(L)(2)](3+)配合物中，Co(III)被两个双齿L配体和两个Tab配体八面体络合。在10中，Co(II)采用扭曲的三角-双锥构型，由一个Cl(-)，一个Tab配体和一个三齿bdmppy配位。在2-6的形成中，当[Zn(Tab)(4)](2+)受到L配体的攻击时，两个Tab配体被从[Zn(Tab)(4)](2+)配体上移除，而在7-9的情况下，[Zn(Tab)(4)](2+)的锌(II)被Co(III)(由O(2)氧化Co(II)得到)所取代，然后通过L配体移除两个Tab配体。在10的情况下，[Zn(Tab)(4)](2+)的中心锌(II)被Co(II)取代，然后通过一个Cl(-)和一个三齿bdmppy除去三个Tab配体。这些配体和金属置换反应可能会提供一些有趣的信息，关于锌-MTS的[锌(S-半胱氨酸)(4)](2-)单元与N-杂环配体和有毒金属离子在自然环境中的相互作用。
Reactions of [Zn(Tab)(4)](PF(6))(2) (Tab = 4-(trimethylammonio)benzenethiolate) (1) with 2,2'-bipyridine (2,2'-bipy), 1,10-phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (2,9-dmphen), N-methylimidazole (N-Meim), and 2,6-bis(pyrazol-3-yl)pyridine (bppy) or with CoCl(2)·6H(2)O at the presence of N-donor ligands (2,2'-bipy, phen, 4,4'-dimethyl-2,2'-bipyridine (4,4'-dmbpy), 2,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (bdmppy))gave rise to a family of zinc or cobalt thiolate complexes, [Zn(Tab)(2)(L)](PF(6))(2) (2: L = 2,2'-bipy, 3: L = phen, 4: L = 2,9-dmphen), [Zn(Tab)(2)(N-Meim)(2)](PF(6))(2) (5), [Zn(Tab)(2)(bppy)](PF(6))(2) (6), [Co(Tab)(2)(L)(2)](PF(6))(3) (7: L = 2,2'-bipy, 8: L = phen, 9: L = 4,4'-dmbpy), and [Co(Tab)(bdmppy)Cl](PF(6)) (10). These compounds were characterized by elemental analysis, IR spectra, UV-vis spectra,(1)H NMR, electrospray ionization (ESI) mass spectra, and single-crystal X-ray diffraction. The Zn(II) in [Zn(Tab)(2)L(n)](2+)dications of 2-5 is tetrahedrally coordinated by two Tab ligands and one L or two N-Meim ligands. In 6, the Zn(II) has a distorted trigonal-bipyramidal geometry, coordinated by two Tab ligands and one tridentate bppy ligand. The Co(III) in the [Co(Tab)(2)(L)(2)](3+) trications of 7-9 is octahedraly chelated by two bidentate L ligands and two Tab ligands. In 10, the Co(II) adopts a distorted trigonal-bipyramidal geometry, coordinated by one Cl(-), one Tab ligand, and one tridentate bdmppy. In the formation of 2-6, two Tab ligands are removed from the [Zn(Tab)(4)](2+) dication when it is attacked by L ligands, while in the cases of 7-9, the Zn(II) of the [Zn(Tab)(4)](2+) dication was replaced by Co(III) (derived from oxidation of Co(II) by O(2)) followed by the removal of two Tab ligands via L ligands. In the case of 10, the central Zn(II) of the [Zn(Tab)(4)](2+) dication was displaced by Co(II) followed by the removal of three Tab ligands via one Cl(-) and one tridentate bdmppy. These ligand and metal replacement reactions may provide some interesting information on the interactions of the [Zn(S-Cys)(4)](2-) unit of Zn-MTs with N-heterocyclic ligands and toxic metal ions encountered in a natural environment.