Departament de Química Inorgànica, Universitat de Barcelona, Av. Diagonal 645, 08028 Barcelona, Spain.
Chemistry. 2012 Mar 19;18(12):3637-48. doi: 10.1002/chem.201102987. Epub 2012 Feb 15.
A series of nickel complexes with nuclearity ranging from Ni(3) to Ni(6) have been obtained by treatment of a variety of nickel salts with the 2-pyridylcyanoxime ligand. The reported compounds have as a common structural feature the triangular arrangement of nickel cations bridged by a central μ(3)-oxo/alkoxo ligand. These compounds are simultaneously the first nickel derivatives of the 2-pyridylcyanoxime ligand and the first examples of isolated, μ(3)-O triangular pyridyloximate nickel complexes. Magnetic measurements reveal antiferromagnetic interactions promoted by the μ(3)-O and oximato superexchange pathways and comparison of the experimental structural and magnetic data with DFT calculations give an in-depth explanation of the factors that determine the magnetic interaction in this kind of system.
一系列核数从 Ni(3) 到 Ni(6) 的镍配合物通过用 2-吡啶基氰肟配体处理各种镍盐而得到。所报道的化合物具有一个共同的结构特征，即镍阳离子以三角形排列，由一个中心 μ(3)-氧/烷氧基配体桥接。这些化合物同时是 2-吡啶基氰肟配体的第一个镍衍生物，也是孤立的 μ(3)-O 三角形吡啶氧肟酸镍配合物的第一个例子。磁性测量显示 μ(3)-O 和肟基超交换途径促进的反铁磁相互作用，以及实验结构和磁性数据与 DFT 计算的比较，深入解释了决定这种系统中磁相互作用的因素。
