| Project/Area Number |
13440200
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | KANAZAWA UNIVERSITY (2003)
Osaka City University (2001-2002) |
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Principal Investigator |
ISOBE Kiyoshi KANAZAWA UNIVERSITY, GRADUATE SCHOOL OF SCIENCE AND TECHNOLOGY, ASSOCIATE PROFESSOR, 自然科学研究科, 教授 (70101285)
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| Co-Investigator(Kenkyū-buntansha) |
HAYASHI Yoshihito KANAZAWA UNIVERSITY, GRADUATE SCHOOL OF SCIENCE AND TECHNOLOGY, ASSOCIATE PROFESSOR, 自然科学研究科, 助教授 (10231531)
NISHIOKA Takanori OSAKA CITY UNIVERSITY, GRADUATE SCHOOL OF SCIENCE, ASSOCIATE PROFESSOR, 大学院・理学研究科, 講師 (10275240)
木下 勇 大阪市立大学, 大学院・理学研究科, 助教授 (80128735)
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| Project Period (FY) |
2001 – 2003
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| Project Status |
Completed (Fiscal Year 2003)
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| Budget Amount *help |
¥16,200,000 (Direct Cost: ¥16,200,000)
Fiscal Year 2003: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 2002: ¥4,100,000 (Direct Cost: ¥4,100,000)
Fiscal Year 2001: ¥9,600,000 (Direct Cost: ¥9,600,000)
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| Keywords | Inorganic Sulfur Cycle / Dinuclear Rhodium Complexes / Disulfido / Oxysulfido Complexes / Reduction of Sulfur Oxides / Thiolsulfonato Complexes / α-Disulfone Complexes / α-Disulfoxido Complexes / C-Cl結合の活性化 / ジチオカルボキシラト錯体 / 結晶相可逆異性化反応 / ロジウム二核錯体 / S-S結合挿入反応 / 結晶相光異性化 / ジスルフィド錯体 / 硫黄の酸化過程 / 硫黄酸化物の還元過程 / 可逆結晶相異性化反応 / NO / 硫黄循環 / 結晶相反応 / 光異性化 / 求電子反応 |
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| Research Abstract |
Inorganic sulfur species with oxidation states between -2 and +6 have been isolated as the ligands in the rhodium dinuclear complexes from the oxygenation of disulfido complex [(RhCp^*)_2(μ-CH_2)_2(μ-S_2)] (1)with O_2 in the air. The isolated oxysulfur complexes are the thiolsulfinato complex [(RhCp^*)_2(μ-CH_2)_2(μ-SSO)] (2),thiolsulfonato complex [(RhCp^*)_2(μ-CH_2)_2(μ-SS(O)_2)] (3),α-disulfoxido complex cis-[(RhCp^*)_2(μ-CH_2)_2(μ-S(O)SO)] (4),and traps-[(RhCp^*)_2(μ-CH_2)_2(μ-S(O)SO)] (5).Using peroxides such as m-CPBA, complex 1 as well as 2 and 3 gave the α-disulfone complex [(RhCp^*)_2(μ-CH_2)_2(μ-S(O)_2SO_2)] (6).These dinuclear complexes have a dithiodirhodium metalacycle framework where the S-S moiety coordinates to the Rh-Rh group in a side-on fashion. The strong electron donation group of Cp^*Rh-RhCp^* allows the high grade oxygenated sulfur species of α-disulfone to work still as the didentate ligand through both S atoms. In this research the reactivity of the isolated oxysulfur complexes towards electrophiles and nucleophiles has been explored. Complex 6 is readily reduced to 3 by NaBH_4, not to 1. Although we did not succeed yet in the reduction of 3 to 1, but found that the reaction of 3 with I_2 or ICH_2CH_2I produces the precursor of 1, [{(RhCp^*)_2(μ-CH_2)_2}_2(μ_4-S_4)]^<2+>. The artificial sulfur cycle on the Rh-Rh bond is completed.
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