Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany.
Dalton Trans. 2009 Nov 14(42):9291-7. doi: 10.1039/b910660j. Epub 2009 Sep 11.
The new ligands, 1-(4-isopropyl phenyl)-4-(2-pyridyl)-1,2,3-triazole, 1 and 1-(mesityl)-4-(2-pyridyl)-1,2,3-triazole, 2 were prepared by the reactions of the respective azides with 2-ethynylpyridine following the "click method". These ligands together with the reported ligands 1-(phenyl)-4-(2-pyridyl)-1,2,3-triazole, 3 and 1-(benzyl)-4-(2-pyridyl)-1,2,3-triazole, 4 were reacted with palladium and platinum precursors to give mononuclear cis-dichloropalladium and platinum complexes containing the triazole ligands. Structural characterisation of the free ligand 3 shows that the central N-N bond in the triazole ring has double bond character and hence is best described as an "azo-like" N-N double bond. The pyridine ring in 3 has an almost "anti" conformation with respect to the central triazole ring. The metal centers bind to the ligands through the pyridine N and a triazole N atom. The metal-N(triazole) distances are shorter than the metal-N(pyridine) distances. Cyclic voltammograms of the ligands show reduction processes that appear at extreme negative potentials. Coordination of metal centers induces huge anodic shifts of the reduction potentials due to sigma-polarisation by the metal centers. UV/Vis spectra of the ligands and complexes are also discussed. The properties of such chelating triazole ligands towards palladium and platinum centers is being compared and contrasted to the widely used 2,2'-bipyridine ligand.
新的配体 1-(4-异丙基苯基)-4-(2-吡啶基)-1,2,3-三唑(1)和 1-(间三甲苯基)-4-(2-吡啶基)-1,2,3-三唑(2)是通过各自的叠氮化物与 2-乙炔基吡啶在“点击法”下反应制备的。这些配体与报道的配体 1-(苯基)-4-(2-吡啶基)-1,2,3-三唑(3)和 1-(苄基)-4-(2-吡啶基)-1,2,3-三唑(4)一起与钯和铂前体反应,得到单核顺式二氯钯和含三唑配体的铂配合物。游离配体 3 的结构表征表明,三唑环中的中心 N-N 键具有双键性质,因此最好描述为“偶氮样”N-N 双键。3 中的吡啶环相对于中心三唑环具有几乎“反式”构象。金属中心通过吡啶 N 和三唑 N 原子与配体结合。金属-N(三唑)距离比金属-N(吡啶)距离短。配体的循环伏安图显示出出现在极端负电位的还原过程。由于金属中心的 sigma 极化,金属中心的配位诱导还原电位发生巨大的阳极位移。配体和配合物的紫外/可见光谱也进行了讨论。正在比较和对比此类螯合三唑配体对钯和铂中心的性质与广泛使用的 2,2'-联吡啶配体。