Binuclear Ni(II) complexes based on bridging oxalate and tetracyanometallates. Synthesis, crystal structure and magnetic properties

Muga I.; Gutierrez-Zorrilla JM.; Vitoria P.; Roman P.; Lloret F.

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Binuclear Ni(II) complexes based on bridging oxalate and tetracyanometallates. Synthesis, crystal structure and magnetic properties

机译：基于桥接草酸酯和四氰基金属酸酯的双核Ni（II）配合物。合成，晶体结构和磁性

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The trimeric complexes, [{Ni(dien)}(2)(mu-ox){mu-Pd(CN)(4))}] (2) and [(Ni(dien)}(2)(mu-ox){(mu-PT(CN)(4))}] (3) were synthesised by the reaction of [{Ni(dien)(H2O)}(2)(mu-ox)](PF6)(2)(.)2H(2)O (dien = dietylenetriamine and ox = oxalate) with K2Pd(CN)(4) and K2Pt(CN)(4), respectively. In this reaction, water substitution and molecular reconstruction reactions take place to afford trimer complexes. These compounds are isostructural with the molecular compound [{Ni(dien)}(2)(mu-ox){(mu-Ni(CN)(4))}] (1). In each complex, the two octahedrally coordinated Ni atoms are oxalate bridged and the sphere of coordination of each Ni is completed by three nitrogen atoms from a diethylenetriamine ligand in fac arrangement and one nitrogen atorn from a bridging cyanide ligand, which belongs to the corresponding square-planar complex [M(CN)(4)](2-). The three compounds present antiferromagnetic behaviour. The magnetic coupling between the two nickel atoms might occur through both bridges, but the length of the exchange pathway through the bidentate tetracyanometallate ligands is large enough to predict that the magnetic interaction may take place mainly through the oxalate ligand. The values of this coupling are similar J (cm(-1)) = -31.2 (1), -33.5 (2) and -33.6 (3). (C) 2002 Elsevier Science Ltd. All rights reserved. [References: 65]

机译：三聚体复合物[{Ni（dien）}（2）（mu-ox）{mu-Pd（CN）（4））}]（2）和[（Ni（dien）}（2）（mu-ox ）{（mu-PT（CN）（4））}]（3）是通过[{Ni（dien）（H2O）}（2）（mu-ox）]（PF6）（2）（）分别与K2Pd（CN）（4）和K2Pt（CN）（4）形成2H（2）O（dien =二甲苯三胺和ox =草酸盐）在该反应中，发生水取代和分子重构反应以生成三聚体这些化合物与分子化合物[{Ni（dien）}（2）（mu-ox）{（mu-Ni（CN）（4））}]（1）是同构的。在每个络合物中，两个八面体配位的Ni原子是草酸盐桥连的，每个Ni的配位范围由二亚乙基三胺配体以fac排列的三个氮原子和桥接氰化物配体产生的一个氮原子完成，后者属于相应的方形-平面络合物[M（CN ）（4）]（2-）。这三种化合物呈现反铁磁行为。两个镍原子之间的磁耦合可能会通过两个桥发生，但长通过二齿四氰基金属酸酯配体的交换路径的h足够大，以预测磁性相互作用可能主要通过草酸酯配体发生。此耦合的值类似J（cm（-1））= -31.2（1），-33.5（2）和-33.6（3）。（C）2002 Elsevier ScienceLtd。保留所有权利。 [参考：65]

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《Polyhedron: The International Journal for Inorganic and Organometallic Chemistry》 |2002年第26期|共8页
作者
Muga I.; Gutierrez-Zorrilla JM.; Vitoria P.; Roman P.; Lloret F.;
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正文语种 eng
中图分类化学;
关键词
Nickel; Palladium; Platinum; Oxalate; Crystal structures; Magnetic properties; Dft calculations; Effective core potentials; Generalized gradient approximation; Dinuclear complexes; Molecular calculations; Exchange interaction; Ligands; Network; Atoms; Transition; Orbitals;

机译：镍;钯;铂;草酸盐;晶体结构;磁性;Dft计算;有效核心势;广义梯度逼近;双核络合物;分子计算;交换相互作用;配体;网络;原子;跃迁;轨道;

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Binuclear Ni(II) complexes based on bridging oxalate and tetracyanometallates. Synthesis, crystal structure and magnetic properties

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