Development of novel photocatalytic system for nitrogen monoxide gas decomposition over polypyrazolylboratocopper (I) complexes

非负性聚吡唑硼酸盐[BRpz_3]^- （pz=1-吡唑基）在络合上作为立体体积大的三齿配体，并已被证明在各种过渡金属有机金属配合物上具有相当大的稳定性。鉴于取代吡唑易于获得，近年来在该三脚配体体系的吡唑环上引入了各种取代基，以期调整配合物中中心金属离子建立的反应场的电子和空间性质。在本项目中，制备了许多取代的聚吡唑硼铜(I)配合物，本课题研究了用一氧化氮（NO）气体处理这些配合物，计算铜(I) NO加合物的分子轨道，用聚苯乙烯载体固定化聚吡唑硼铜基团。(1)利用各种取代吡唑，得到了许多含取代聚吡唑硼酸基团的钾盐和铜(I)配合物。揭示了它们的光谱性质、物理化学性质和结构特征。(2)用NO气体处理铜(I)配合物，并对形成的NO加合物进行了光谱研究。取代基引入效应对NO加合物的稳定性有显著影响。(3)铜(I) NO加合物[Cu{BH(3-^tBupz)_3}(NO)]在低温下具有显著的稳定性。根据Tolman报道的晶体结构数据，本研究人员对该加合物进行了EHMO计算，并对计算结果进行了表征。(4)通过聚苯乙烯的溴化、丁基锂的锂化、对二羟基硼基聚苯乙烯的生成，制备了聚合度约为38的聚苯乙烯固载聚吡咯酸钠。

Uninegative polypyrazolylborates [BRpz_3]^- (pz=1-pyrazolyl) serve as sterically bulky tridentate ligands on complexation, and have been shown to confer considerable stability on a variety of transition-metal organometallic complexes. In view of easy access to substituted pyrazoles, introduction of various substituents has been carried out into the pyrazolyl rings of this tripodal ligand system in these years, with the hope of finetuning the electronic and steric properties of reaction fields built up on the central metal ions in the complexes. In this project, many substituted polypyrazolylboratocopper (I) complexes have been prepared, and the present researcher studied treatment of these complexes with nitrogen monoxide (NO) gas, molecular orbital calculation of a copper (I) NO-adduct, immobilization of polypyrazolylborato groups with polystirene supports.(1) By use of various substituted pyrazoles, many potassium salts and copper (I) complexes were obtained with substituted polypyrazolylborato groups. Their spectroscopic properties, physical chemistry, and structural characteristics have been revealed.(2) Treatment of the copper (I) complexes with NO gas was performed, and NO adducts formed were studied spectroscopically. Substituent introduction effects into the pyrazolyl rings, were noteworthy on the stabilities of the NO adducts.(3) Tne copper (I) NO-adduct, [Cu{BH(3-^tBupz)_3}(NO)] is significantly stable at low temperatures. From its crystal structural data reported by Tolman, the present researcher carried out the EHMO calculations for the adduct, and subsequent characterization of the calculation results is underway.(4) Sodium polypyrazolylborate immobilized on polystirene (polymerization degree, ca.38) was prepared through polystirene bromination, lithiation with butyl lithium, and formation of p-(dihydroxyboryl) polystirene.