| Project/Area Number |
15205009
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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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 | Tokyo Institute of Technology |
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Principal Investigator |
SUZUKI Hiroharu Tokyo Institute of Technology, Graduate School of Science and Engineering, Professor, 大学院理工学研究科, 教授 (30106629)
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| Co-Investigator(Kenkyū-buntansha) |
TAKAO Toshiro Tokyo Institute of Technology, Graduate School of Science and Engineering, Assistant Professor, 大学院理工学研究科, 助手 (00313346)
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| Project Period (FY) |
2003 – 2005
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥42,770,000 (Direct Cost: ¥32,900,000、Indirect Cost: ¥9,870,000)
Fiscal Year 2005: ¥8,710,000 (Direct Cost: ¥6,700,000、Indirect Cost: ¥2,010,000)
Fiscal Year 2004: ¥9,360,000 (Direct Cost: ¥7,200,000、Indirect Cost: ¥2,160,000)
Fiscal Year 2003: ¥24,700,000 (Direct Cost: ¥19,000,000、Indirect Cost: ¥5,700,000)
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| Keywords | nitrogen fixation / cluster complex / ruthenium / nitrogen reduction / ammonia / heterometallic cluster complex / アンモニア活性化 / ポリヒドリドクラスター / ルテニウム錯体 / 架橋オキソ配位子 / 窒素-窒素結合切断 / アゾ化合物 / ニトリル活性化 / 窒素-炭素結合切断 / ヒドリド錯体 / ルテニウムクラスター / ヒドラジン / アゾベンゼン / 水素化 / 窒素分子活性化 / 窒素固定 / ルテニウムヒドリドクラスター / カチオン性ポリヒドリド錯体 / 置換ヒドラジン / 三重架橋イミド錯体 |
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| Research Abstract |
The reactivity of transition metal cluster complexes has been of special interest in anticipation of their remarkable reactivity due to the synergy of adjacent metal centers. Transition metal cluster complex, especially, metal polyhydrido cluster not only has many hydrogen atoms in the core of the cluster but also has an intrinsic property of transferring multiple electrons between the cluster and the coordinated substrate, the polyhydrido cluster likely promotes the nitrogen reduction to ammonia in the absence of both a proton source and a reducing agent. The primary aim of this research project was the reaction chemistry of hydrazine derivatives with metal cluster to elucidate details of the transition metal-assisted nitrogen reduction. Synthesis of heterometallic clusters containing a relatively Lewis-acidic metal was also an important object of the research.
The main results of the research are as follows : (1) cleavage of nitrogen-nitrogen bonds of ammonia induces by triruthenium polyhydrido clusters, ^1 (2) nitrogen-nitrogen double bond cleavage of azobenzene by a triruthenium polyhydrido complex, and catalytic hydrogenation of azobenzene and 1,2-diphenylhydrazine, ^2 (3) reductive cleavage of the N-N bond of hydrazine induced by a cationic trinuclear ruthenium hexahydrido complex, ^3 (4) nitrogen-nitrogen bond cleavage of hydrazine derivatives by trinuclear pentahydride complex of ruthenium, ^4 (5) synthesis and structure of a trinuclear complex containing a face-capping pyridine ligand, ^5 (6) cleavage of the C -N triple bond on the triruthenium cluster, ^6 (7) synthesis of group 8-group 6 heterotrimetallic polyhydrido complexes having only a C_5Me_5 group as auxiliary ligand, ^7 (8) synthesis and reaction of a heterobimetallic polyhydride complex containing ruthenium and osmium with ethylene, ^8 (9) di- and trinuclear polyhydride complexes containing ruthenium and rhenium. ^9
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