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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Stepwise construction of mono-, di- and tri-nuclear 2:1, 1:2, 2:3 ligand: mixed-metal complexes using a bis-tridentate bridging ligand
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Stepwise construction of mono-, di- and tri-nuclear 2:1, 1:2, 2:3 ligand: mixed-metal complexes using a bis-tridentate bridging ligand

机译：使用双三齿桥联配体逐步构建单核，二核和三核2：1、1：2、2：3配体：混合金属配合物

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摘要

Extended molecular structures have been constructed with the bis-tridentate ligand N,N,N',N'-tetrakis (2-pyridyl-methyl) benzene-1,4-diamine (tpbd), and the bis-tridentate, metal 'complex' ligand, [Ru(tpbd)_2](PF_6)_2 (1) as building blocks. The ligand tpbd and complex 1 react analogously with Cu(II) salts to yield the corresponding di-and trinuclear aqua complexes, [Cu_2(tpbd)(H_2O)_4] (ClO_4))_4 (2a) and [Cu_2Ru(tpbd)_2(H_2O)_4](BF_4)_4(PF_6)·2H_2O (3a). The labile water ligands in thee complexes have been replaced by other solvents or 2,2'-bipyridine (bipy). In the latter case the mixed ligand complexes [Cu_2(tpbd)(bipy)_2](PF_6)_4·2H_2O (2b) and [Cu_2Ru(BF_4)_2(bpbd)_2(bipy)_2](PF_6)_4·2H_2O (3b) respectively are obtained. These reactions represent prototype substitutions for the controlled stepwise evolution of even larger molecular entities. Recrystallisation of 3a in 2% NaBF_4 methanol/water solution, resulted in crystals of [Cu_2Ru(tpbd)_2(H_2O)_4](BF_4)_4(PF_6)_2·8H_2O (3a'). Recrystallisation of 3b in 2% NaBF_4 CH_3CN/water solution gave [Cu_2Ru(BF_4)_2(tpbd)_2(bipy)_2](BF_4)_2(PF_6)_2·H_2O (3b'). The X-ray structures of the mononuclear and trinuclear ruthenium-containing complexes (1,3a', 3b') show cis-fac six-coordinate geometries around the Ru atoms. As a consequence thep henylene groups of the tpbd ligands are approximately perpendicular to each other. In the trinuclear Ru-Cu_2 complexes the copper atoms are located anti to each other about the [(tpbd)Ru(tpbd)]~(2+) building block. The flexibility of tpbd is demonstrated by the geometries of the copper coordinated ends of tpbd, which are coordinated meridionally in 3a', but facially in 3b'. Solution spectroscopy, and the detection of appropriate ions by mass spectrometry, show that the dicopper and trinuclear copper-ruthenium complexes are present in solution. UV-Visible spectroscopy, EPR and cyclic voltammetry indicate that there is insignificant electronic communication between the metal centers in the di-and tri-nuclear complexes since sali8ent metal-based features are additive.
机译：用双三齿配体N，N，N'，N'-四（2-吡啶基甲基）苯-1,4-二胺（tpbd）和双三齿金属'复合物'构建了扩展的分子结构配体，[Ru（tpbd）_2]（PF_6）_2（1）作为结构单元。配体tpbd和配合物1与Cu（II）盐类似反应，生成相应的二核和三核水配合物[Cu_2（tpbd）（H_2O）_4]（ClO_4））_ 4（2a）和[Cu_2Ru（tpbd）_2 （H_2O）_4]（BF_4）_4（PF_6）·2H_2O（3a）。这些络合物中不稳定的水配体已被其他溶剂或2,2'-联吡啶（联吡啶）取代。在后一种情况下，混合配体配合物[Cu_2（tpbd）（bipy）_2]（PF_6）_4·2H_2O（2b）和[Cu_2Ru（BF_4）_2（bpbd）_2（bipy）_2]（PF_6）_4·2H_2O（分别获得3b）。这些反应代表了更大分子实体受控逐步进化的原型替代。 3a在2％NaBF_4甲醇/水溶液中重结晶，生成[Cu_2Ru（tpbd）_2（H_2O）_4]（BF_4）_4（PF_6）_2·8H_2O（3a'）晶体。 3b在2％NaBF_4 CH_3CN /水溶液中的重结晶得到[Cu_2Ru（BF_4）_2（tpbd）_2（bipy）_2]（BF_4）_2（PF_6）_2·H_2O（3b'）。单核和三核含钌配合物（1,3a'，3b'）的X射线结构显示Ru原子周围的顺式六坐标几何结构。结果，tpbd配体的对亚苯基大约彼此垂直。在三核Ru-Cu_2络合物中，铜原子位于[（tpbd）Ru（tpbd）]〜（2+）结构单元之间彼此相反。 tpbd的柔韧性由tpbd的铜配位末端的几何形状证明，这些配位在3a'中经向协调，但在3b'面经协调。溶液光谱法以及通过质谱检测合适的离子表明，溶液中存在双铜和三核铜-钌络合物。紫外可见光谱法，EPR和循环伏安法表明，二核和三核配合物中的金属中心之间没有明显的电子通讯，因为重要的基于金属的特征是可加的。

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