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)作为立体大体积的三齿配体用于络合，已被证明对各种过渡金属有机金属配合物具有相当大的稳定性。鉴于取代吡唑的易得性，近年来，人们在该三脚架配体体系的吡唑环上引入了各种取代基，以期微调中心金属离子上形成的反应场的电子和空间性质。在本项目中，我们制备了许多取代的聚吡唑基硼铜(I)络合物，并研究了这些络合物在氮氧化物(NO)气体中的处理、铜(I)的NO-加合物的分子轨道计算、聚二茂铁载体固定聚吡唑基硼(I)基团。(1)通过使用各种取代的吡唑，得到了许多钾盐和铜(I)的络合物。揭示了它们的光谱性质、物理化学和结构特征。(2)对不含气体的铜(I)络合物进行了处理，用光谱学方法研究了不生成加合物的情况。取代基引入吡唑环对NO加合物的稳定性有重要影响。(3)铜(I)NO加合物[Cu{BH(3-^tBupz)_3}(NO)]在低温下非常稳定。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)聚合度约38的聚吡唑硼酸钠是通过聚苯乙烯溴化、丁基锂锂硫化和对二羟基硼聚苯乙烯的形成而制备的。

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.