首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Trinuclear and tetranuclear manganese clusters derived from cyano(imino(methoxy)methyl)nitrosomethanide (cmnm)
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Trinuclear and tetranuclear manganese clusters derived from cyano(imino(methoxy)methyl)nitrosomethanide (cmnm)

机译:氰基(亚氨基(甲氧基)甲基)亚硝基锰(cmnm)衍生的三核和四核锰簇

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Three manganese clusters have been synthesised via the reaction of Mn~(II) with cyano(imino(methoxy) methyl)nitrosomethanide (cmnm), obtained from the in situ nucleophilic addition of MeOH to dicyanonitrosomethanide (dcnm). X-ray crystallographic studies show that the complex [Mn~(II) _3(cmnm)6]·MeOH (1) is a linear trinuclear species, with a central octahedral and two outer trigonal-prismatic manganese(II) ions. Two mixed-valent tetranuclear complexes [Mn~(II) _2Mn~(III) _2O_2(cmnm)_4Cl_2(MeOH)_6] (2) and [Mn~(II) _2Mn~(III) _(2-) O_2(cmnm)_4Cl_2(MeOH)_4(pzH)_2]·2MeOH (3) (pzH = pyrazole) contain two Mn~(II) and two Mn~(III) ions in butterfly- type structures, with the six-coordinate 'body' Mn~(III) ions bridged to the seven-coordinate 'wingtip' Mn~(II) ions by Ч3-O~(2-) and by nitroso oxygen atoms of the cmnm ligands. The formation of the trinuclear and tetranuclear manganese clusters is dependent on the stoichiometry used in the reactions. Solid state DC magnetic susceptibility studies on complexes 1 and 3 reveal that antiferromagnetic interactions are dominant within the clusters. Fits of the data reveal an S = 5/2 ground state for 1 and a S = 0 ground state for 3, with several close lying excited states found in both cases.
机译:通过Mn〜(II)与氰基(亚氨基(甲氧基)甲基)亚硝基锰(cmnm)的反应合成了三个锰簇,这是通过将甲醇原位亲核加成到二氰基亚硝基甲烷(dcnm)中获得的。 X射线晶体学研究表明,复合物[Mn〜(II)_3(cmnm)6]·MeOH(1)是线性三核物种,具有中心八面体和两个外部三角棱晶锰(II)离子。两种混合价四核配合物[Mn〜(II)_2Mn〜(III)_2O_2(cmnm)_4Cl_2(MeOH)_6](2)和[Mn〜(II)_2Mn〜(III)_(2-)O_2(cmnm) )_4Cl_2(MeOH)_4(pzH)_2]·2MeOH(3)(pzH =吡唑)在蝶型结构中包含两个Mn〜(II)和两个Mn〜(III)离子,六坐标的“体” Mn〜(III)离子通过Ч3-O〜(2-)和cmnm配体的亚硝基氧原子与七坐标的“翼尖” Mn〜(II)离子桥接。三核和四核锰簇的形成取决于反应中使用的化学计量。对配合物1和3的固态DC磁化率研究表明,反铁磁相互作用在簇中占主导地位。数据拟合显示出1的S = 5/2基态和3的S = 0基态,在两种情况下都发现了几个密闭的激发态。

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