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

这项工作的目的是制备新的含低价金属的大环配合物。低价金属络合物往往表现出较长的激发态寿命。此外，许多大环化合物具有特殊的性质。因此，含有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，我们在以下三个方面进行了研究：新型大环化合物的合成与表征。合成了一系列新的18元呋喃大环化合物，并对其结构进行了表征。化合物的结构取决于大环中包含的金属原子。含双膦配体的低价金属配合物的光化学研究具有三重Dekker型结构。配合物铂(BINAP)_2(BINAP=1，1‘-双(二苯基膦)-2，2’-联苯基)在可见光区有吸收和发光。通过对发光的猝灭研究，探讨了该络合物与卤代烃的光化学反应机理。提出了该光化学反应的电子转移机理。此外，还观察了醇与含双膦配体的铂、钯配合物在光照下的反应生成羰基化合物。含贵金属的新型大环配合物的合成。我们去年通过1-溴-2，6-双(溴甲基)苯与1，3-二氨基丙烷反应合成了一种新的大环化合物。其结构经核磁共振和X-射线衍射法确证。还制备了含锂离子的大环。最后，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.