The synthesis of the macrocyclic complexes containing low-valent metals.

本工作的目的是制备新的含低价金属的大环配合物。低价金属配合物往往表现出较长的激发态寿命。此外，许多大环配合物具有特殊的性质。因此，含低价金属的大环化合物有望具有有趣的性质。为了达到这一目的，我们对以下三个主题进行了研究。新型大环配合物的合成与表征。制备了一系列新的含呋喃基团的18元大环配合物，并对其结构进行了表征。配合物的结构取决于包含在大环中的金属原子。铷配合物具有新颖的三层结构。含二膦的低价金属配合物的光化学性质。配合物Pt (binap)_2, （binap=1,1′-双（二苯基膦）-2,2′-二苯基）在可见光区表现出吸收和发光。通过发光猝灭研究，探讨了配合物与卤代烃的光化学反应机理。提出了光化学反应的电子传递机理。此外，还观察了醇与含二膦的铂配合物或钯配合物在光照射下反应生成羰基化合物。含贵金属的新型大环配合物的合成。去年我们用1-溴-2,6-二（溴乙基）苯与1,3-二氨基丙烷反应得到了一个新的大环化合物。通过核磁共振和x射线的方法对其结构进行了澄清。制备了含锂离子的大环。最后，首次合成了大环配体的钯配合物并对其进行了表征。

The aim of the work is to prepare the new macrocyclic complexes containing low-valent metals. low-valent metal complexes often show a long lifetime of the excited state. Further, many macrocyclic complexes have peculiar properties. Thus macrocyclic compound containing low-valent metals are expected to posses interesting properties. In order to accomplish the purpose, we have made studies on the following three subjects.The synthesis and characterization of new macrocyclic complexes. A series of new 18-membered macrocyclic complexes containing furane groups have been prepared and structurally characterized. The structures of the compexes depend on the metal atoms included in the macrocycles. The rubidium complex has a novel triple-dekker type structurePhotochemistry of low-valent metal complexes containing diphosphines. The complex, Pt (binap)_2, (binap=1,1'-bis (diphynylphosphono) -2,2'-binaphtyhyl) shows absorption and luminescence in the visible region. The mechanism of the photochemical reaction of the complex with alkyl halides was explored by the quenching study of the luminescence. An electron-transfer mechanism is proposed for the photochemical reaction. Further, the reaction of alcohols with the platinum complex or the palladium complex containing diphosphines were observed under irradiation of light to give carbonyl compounds.The synthesis of new macrocyclic complexes containing noble metals. We have obtained a new macrocyclic compound by the reaction of 1-bromo-2,6-bis (bromomethyl) benzene with 1,3-diaminopropane last year. The structure was clarified by NMR and X-ray methods. The macrocycle containing lithium ion was also prepared. Finally, the palladium complex of the macrocyclic ligand was synthesized and characterized for the first time.