Oligonuclear nickel(II) complexes sustained by intermolecular hydrogen-bonding
Oligonuclear nickel(II) complexes sustained by intermolecular hydrogen-bonding
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由分子间氢键维持的寡核镍(II)络合物
DOI：
10.1016/j.ica.2004.03.054
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发表时间：
2004
期刊：
影响因子：
--
通讯作者：
P. E. McHugh
中科院分区：
文献类型：
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作者：
H. Adams;D. Fenton;P. E. McHugh
在NaPF_6存在下，Ni（OAc）_2与对称的“末端关闭”隔室前配体2，6-[N，N′-双（2-羟基苯甲基）-N，N′-双（2-吡啶甲基）氨甲基]-4-甲基苯酚（H_3L）反应生成了一种同四核镍（II）配合物[（Ni_4 HL）（L）（OAc）_2（H_2O）_2（HOAc）_2] PF_6.该配合物的晶体结构表明，该配合物是供体不对称的，并且扩展的超配体外围通过相邻配体的两个侧链苯酚/苯氧基之间的紧密氢键以及配位乙酸分子与配体的其余侧链苯酚之间的进一步紧密氢键来维持，产生[CH 3COO <$H <$LH <$L <$H <$OOCCH3]5−类型的复酸盐。在甲醇中，H3 L与Ni（OAc）2和NaClO 4反应，得到配合物[Ni 2（HL）（OAc）2（OH 2）2][ClO 4]。通过X射线衍射确定了配合物的结构，表明配合物以分子间氢键促进的二聚体形式存在。
Reaction of Ni(OAc)2with the symmetric `end-off' compartmental proligand 2,6-[N,N′-bis(2-hydroxy-phenylmethyl)-N,N′-bis(2-pyridylmethyl)aminomethyl]-4-methylphenol (H3L) in the presence of NaPF6has been found to generate a homotetranuclear nickel(II) complex [(Ni4HL)(L)(OAc)2(H2O)2(HOAc)2]PF6. The crystal structure of the complex reveals that the complex is donor asymmetric and that the extended supra-ligand periphery is maintained by a tight hydrogen-bond between two pendant phenol/phenoxy groups of adjacent ligands and by further tight hydrogen-bonds between coordinated acetic acid molecules and the remaining pendant phenols of the ligand, generating a double acid salt of the type [CH3COO⋯H⋯LH⋯L⋯H⋯OOCCH3]5−. Reaction of H3L with Ni(OAc)2and NaClO4in methanol gave the complex [Ni2(HL)(OAc)2(OH2)2][ClO4]. The structure was determined by X-ray diffraction and showed that the complex exists as a dimer promoted by intermolecular hydrogen-bonding.