| Project/Area Number |
11640617
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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 |
分離・精製・検出法
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| Research Institution | Kansai University |
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Principal Investigator |
ARAKAWA Ryuichi Kansai University, Faculty of Engineering, Professor, 工学部, 教授 (00127177)
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| Project Period (FY) |
1999 – 2000
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 2000: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1999: ¥1,700,000 (Direct Cost: ¥1,700,000)
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| Keywords | Electrospray / ESI-MS / On-line mass analysis / Ru(II) complex / electrolysis cell / electrolysis / intermediate / photoreaction / 電解反応中間体 |
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| Research Abstract |
Electrospray ionization mass spectrometry (ESI-MS) has an attractive advantage of soft ionization. The ESI technique results in the transfer of ions initially present in solution into the gas phase. So it provides a quite simple mass pattern and allows us to determine molecular mass accurately with high sensitivity. An on-line electrospray ionization mass-spectrometric analysis for an electrolysis reaction was developed by the installation of a compact, efficient flow-through cell upstream of an electrospraying needle. The electrode was designed to avoid any reduction of the oxidation products formed during electrolysis. The electrolytic oxidation reaction of a Ru and Os metal complex was carried out to examine the performance of the system. From the electrolysis of [M(bpy)3](PF6)2 (where M=Ru and Os, and bpy=2,2'-bipyridine) we detected the one-electron oxidation product, [M(bpy)3]3+. The electrolysis of [Ru(bpy)2(en)](ClO4)2 (en=ethylenediamine) formed two complex products along with the elimination of two and four hydrogen atoms from the en ligand. The structure of the two complex products was determined to be a monoimine and diimine complex, based on an electrolysis experiment using a deuterium-labeled complex, [Ru(bpy)2(ed)](ClO4)2 (ed=ethylene-d4-diamine, H2N-CD2-CD2-NH2). The results indicate that electrochemical oxidation occurs at the ethylenediamine ligand and that the monoimine complex is a reaction intermediate for the formation of a diimine complex. In addition, the photo ligand substitution reaction of the bisphenanthroline (phen) complex in acetonitrile solution was studied using the same on-line system. We detected monodentate complexes with the en ligand as an intermediate. The difference in the photochemical reactivity of the bpy and the phen complex can be explained by the difference in configurational flexibility in the Ru(II) complexes.
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