Zinc triad metal ion complexes of NN′S ligand N-(2-pyridylmethyl)-N-(2-(methylthio)ethyl)amine
Zinc triad metal ion complexes of NN′S ligand N-(2-pyridylmethyl)-N-(2-(methylthio)ethyl)amine
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DOI：
10.1080/10241220802144552
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发表时间：
2007-01-01
影响因子：
1.5
通讯作者：
Butcher, Raymond J.
中科院分区：
文献类型：
--
作者：
Bebout, Deborah C.;Lai, Wei;Butcher, Raymond J.
用X射线晶体学和质子核磁共振研究了二价锌三价金属离子与N-（2-吡啶甲基）-N-（2-甲硫基）乙基）胺（L）的配位化学。氯化物盐产生非同源的M（L）Cl-2复合物。Hg（L）Cl-2和Zn（L）Cl-2分别为五配位的畸变四方锥和三角双锥构型。Cd（L）Cl-2形成具有扭曲八面体几何构型的六配位聚合物。这些配合物具有相似的几乎与温度无关的质子NMR谱，表明它们之间的结构差异在溶液中由于流动过程而不太广泛。虽然1：在[M ~（2+）]/[L]范围内，[M（L）（NCCH_3）（x）]（2+）的热力学稳定性仅在[M ~（2+）] >= [L]时超过[M（L）（2）]（2+）。[M（L）（2）]（2+）的分子内和分子间交换条件以及[M（L）（NCCH 3）（x）]（2+）的分子间交换条件在质子化学位移和J（（MH）-H-1）时间尺度上存在。在生理相关温度下，二价锌三元组金属离子和硫醚配体组分之间的强烈相互作用表明，在更全面地了解这些金属离子的生物活性时，应考虑与蛋氨酸的相互作用。
The coordination chemistry of divalent zinc triad metal ions with N-(2-pyridylmethyl)-N-(2-(methylthio)ethyl)amine (L) was investigated by X-ray crystallography and proton NMR. Chloride salts yielded non-homologous M(L)Cl-2 complexes. Hg(L)Cl-2 and Zn(L)Cl-2 were five-coordinate monomers with distorted square pyramidal and trigonal bipyramidal geometries, respectively. Cd(L)Cl-2 formed a six-coordinate polymer with a distorted octahedral geometry. These complexes had similar nearly temperature independent proton NMR spectra suggesting structural differences between them were less extensive in solution due to fluxional processes. Although 1: 1 metal to ligand complexes were most thermodynamically stable for the chloride salts at all [M2+]/[L], the thermodynamic stability of [M(L)(NCCH3)(x)](2+) only exceeded that of [M(L)(2)](2+) when [M2+] >= [L] with perchlorate salts. Slow intramolecular and intermolecular exchange conditions for [M(L)(2)](2+) and slow intermolecular exchange conditions for [M(L)(NCCH3)(x)](2+) were found on the proton chemical shift and in some cases J((MH)-H-1) time scales. Strong interactions between divalent zinc triad metal ions and thioether ligand components at physiologically relevant temperatures suggest interactions with methionine should be considered in developing a more complete understanding of the bioactivities of these metal ions.