1997 Fiscal Year Final Research Report Summary
Development of novel photocatalytic system for nitrogen monoxide gas decomposition over polypyrazolylboratocopper (I) complexes
| Project/Area Number |
08650982
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
工業物理化学
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| Research Institution | Nagasaki University |
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Principal Investigator |
ONISHI Masayoshi Faculty of Engineering, Nagasaki University, Associate Professor, 工学部, 助教授 (00039695)
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| Project Period (FY) |
1996 – 1997
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| Keywords | nitrogen monoxide / copper complex / polypyrazolylborate / photocatalysis / polystirene / macromolecular catalysis |
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| Research Abstract |
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.
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