Preparation, structures and properties of manganese complexes containing amine-(amido or amidato)-phenolato type ligands
Preparation, structures and properties of manganese complexes containing amine-(amido or amidato)-phenolato type ligands
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DOI：
10.1016/j.ica.2016.03.036
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发表时间：
2016-06-01
影响因子：
2.8
通讯作者：
Kawata, Satoshi
中科院分区：
文献类型：
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作者：
Mitsuhashi, Ryoji;Ogawa, Rina;Kawata, Satoshi
研究了2 - 羟基 - N -（n - 氨基烷基）苯甲酰胺（其中n - 氨基烷基取代基为2 - 氨基 - 2 - 甲基丙基（H₂L₂(Me₂)）、(R) - 2 - 氨基丙基{(R) - H₂L₂(Me)}和3 - 氨基丙基（H₂L₃））与氯化锰或高氯酸锰的络合作用。对于2 - 氨基丙基衍生物，分离得到了带有二价阴离子配体的双核甲氧基桥连的锰(III)配合物[{Mn(L₂(Me₂)或(R) - L₂(Me))(MeOH)}₂(μ - OMe)₂]（2或4），并确定了它们的晶体结构。在2中，两个轴向畸变的Mn - III中心之间存在弱的反铁磁相互作用。此外，使用配体(L₂(Me₂))₂，得到了单核锰(IV)配合物[Mn(L₂(Me₂))₂]·DMF（3·DMF）。在3·DMF的晶体中，观察到通过分子间双氢键的异手性二聚作用。在与H₂L₃反应的情况下，得到了单核锰(III)配合物[Mn(H₂L₃')₂Cl₂]Cl（6）和[Mn(H₂L₃')₂(MeOH)₂]Cl₂(ClO₄)（7），其中配体（H₂L₃'）具有H₂L₃的酚盐酰胺 - 铵型两性离子形式，并通过酚氧 - O和酰胺 - O原子与Mn - III中心配位形成六元螯合环。此外，通过单晶X射线衍射研究揭示了一种四核（Mn₂Mn₂III） - Mn - II双不完全立方烷型簇合物[Mn₄(HL₃)₂Cl₂(OMe)₆(MeOH)₂]·4MeOH（5a·4MeOH），尽管从反应混合物中获得的块状晶体（5）显示出不同的粉末X射线衍射（PXRD）图谱。对5的块状晶体的元素分析表明它们由相同的四核簇组成。有趣的是，5的块状晶体高度风化，并且表明它们的配位甲氧基和甲醇配体在大气中分别容易被羟基和水取代。这种转化极大地改变了它们的磁行为。（C）2016 Elsevier B.V.保留所有权利。
Complexation of 2-hydroxy-N-(n-aminoalkyl)benzamides, where n-aminoalkyl substituents are 2-amino-2-methylpropyl (H(2)L2(Me2)), (R)-2-aminopropyl {(R)-H(2)L2(Me)} and 3-aminopropyl (H(2)L3), with manganese(II)chloride or perchlorate were examined. With the 2-aminopropyl derivatives, dinuclear methoxido-bridged manganese(III) complexes bearing the dianionic ligands, [{Mn(L2(Me2) or (R)-L2(Me)) (MeOH)}(2)(mu-OMe)(2)] (2 or 4), were isolated and their crystal structures were determined. There was a weak antiferromagnetic interaction between two axially distorted Mn-III centers in 2. Also, with the ligand of (L2(Me2))(2) a mononuclear manganese(IV)complex, [Mn(L2(Me2))(2)]center dot DMF (3 center dot DMF) was obtained. In the crystal of 3 center dot DMF a heterochiral dimerization via the intermolecular double hydrogen-bonds was observed. In the case of reactions with H(2)L3, mononuclear manganese(III)complexes, [Mn(H(2)L3 ')(2)Cl-2] Cl (6)and [Mn(H(2)L3 ')(2)(MeOH)(2)]Cl-2(ClO4)(7), were afforded, where the ligand (H(2)L3 ')has a phenolateamide-ammonium type zwitterionic form of H(2)L3 and coordinates to a Mn-III center via the phenolato-O and amide-O atoms to form a six-membered chelate ring. Furthermore, a tetranuclear (Mn2Mn2III)-Mn-II double incomplete-cubane type cluster compound, [Mn-4(HL3)(2)Cl-2(OMe)(6)(MeOH)(2)]center dot 4MeOH (5a center dot 4MeOH) was revealed by the single-crystal X-ray diffraction study, although the bulk crystals (5)obtained from the reaction mixture showed a different PXRD pattern. The elemental analysis of the bulk crystals of 5 suggested that they consist of the same tetranuclear clusters. It is interesting that the bulk crystals of 5 were highly efflorescent, and it was suggested that their coordinated MeO and MeOH ligands were easily substituted by OH and H2O, respectively, in atmospheric air. This conversion changed their magnetic behaviors drastically. (C) 2016 Elsevier B.V. All rights reserved.