ynthesis of Macrocyclic Multinuclear Ruthenium Complexes Having an Ability on Catalytic Oxidation by Self-Assembly

利用配位键自组装的多核金属配合物引起了人们的广泛关注，特别是具有疏水空腔的大环多核配合物（可包含有机分子）的主-客体化学得到了广泛的研究。我们的目标是通过自组装的方法制备大环多核钌配合物，特别是具有包合底物的能力和含有活性金属中心的大环多核钌配合物，它们被认为是金属酶的模型。本文尝试了含两个钌和两个钯或铂离子的大环四核配合物的合成。合成了含钌单元的Ru_2 Pd_2大环配合物，该配合物对烷烃的氧化反应具有催化活性。通常情况下，大环配合物的合成主要采用具有顺式配位的桥联配体的金属配合物，但当具有催化活性的金属配合物参与大环配合物时，催化中心的活性位远离所包含的底物。为了克服这一缺陷，设计合成了一种新型的含钌单元的跨配位桥联配体的钌铂大环配合物。

Self-assembled multinuclear metal complexes utilizing coordination bonds draw much attention, especially host-guest chemistry of the self-assembled macrocyclic multi-nuclear complexes having a hydrophobic cavity, which can include a organic molecule, are studies extensively. Our goal is to prepare the macrocyclic multinuclear ruthenium complexes by self-assembly, especially having ability to include the substrate and containing the active metal site, which are considered as the model of metal enzymes. Syntheses of the macrocyclic tetranuclear complexes containing two ruthenium and two palladium or platinum ions have been tried. The Ru2Pd2 macrocyclic complex containing the ruthenium unit, which showed catalytic ability on oxidation of alkanes, was synthesizedIn general, metal complexes with cis-coordinated bridging ligands are employed in the syntheses of macrocyclic complexes, however, the active site of the catalytic center is far away from the included substrate, when the metal complex having catalytic ability is involved in these macrocyclic complexes. The novel Ru2Pt2 macrocyclic complex containing ruthenium unit with transcoordinated bridging ligands was newly designed to overcome this defect and was synthesized.