Institute of Molecular Functional Materials and Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong, China.
Dalton Trans. 2012 May 21;41(19):5794-8. doi: 10.1039/c2dt11810f. Epub 2012 Feb 13.
Reaction of [Ru(VI)(N)(sap)Cl] with excess NaN(3) affords a novel paramagnetic triazidoruthenium(III) complex Ru(III)(sap)(N(3))(3), which is isolated as a PPh(4)(+) salt (1). Reaction of 1 with Ni(2+) and Co(2+) ions produce two isostructural hexanuclear [Ru(4)M(2)] compounds, [Ru(IV)(4)M(II)(2)(μ(3)-OMe)(2)(μ-OMe)(2)(μ-N)(2)(μ-N(3))(2)(μ-O(phenoxy))(2)(sap)(4) (MeOH)(4)] (M = Ni 2 or Co 3). The molecular structures of 1-3 have been determined by X-ray crystallography. 1 is a mononuclear ruthenium(III) compound where three azide ligands are bonded to ruthenium in a meridional fashion, while compounds 2 and 3 are isostructural hexanuclear compounds containing a defective face-sharing dicubane-like core with two missing vertexes. Variable-temperature dc magnetic susceptibility studies have been carried out for 2 and 3. These data indicate that there are four diamagnetic Ru(IV) ions in 2 and 3 and there is ferromagnetic interaction between the two Ni(2+) in 2 and Co(2+) in 3 via the methoxy bridges.
[Ru(VI)(N)(sap)Cl]与过量 NaN(3)反应得到一种新型顺磁性三氮唑钌(III)配合物Ru(III)(sap)(N(3))(3)，其作为 PPh(4)(+)盐(1)被分离出来。1与 Ni(2+)和 Co(2+)离子反应生成两种同构的六核[Ru(4)M(2)]化合物，[Ru(IV)(4)M(II)(2)(μ(3)-OMe)(2)(μ-OMe)(2)(μ-N)(2)(μ-N(3))(2)(μ-O(phenoxy))(2)(sap)(4)(MeOH)(4)] (M = Ni 2 或 Co 3)。1-3 的分子结构通过 X 射线晶体学确定。1 是单核钌(III)化合物，其中三个叠氮配体以轴向方式与钌键合，而化合物 2 和 3 是同构的六核化合物，含有一个有缺陷的面共享双立方烷样核，有两个缺失的顶点。对 2 和 3 进行了变温直流磁导率研究。这些数据表明，2 和 3 中各有四个抗磁性 Ru(IV)离子，并且通过甲氧基桥，2 中的两个 Ni(2+)和 3 中的 Co(2+)之间存在铁磁相互作用。
