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

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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.