Synthesis and Electronic Structure of Group 9 Metal Clusters with Novel Framework
| Project/Area Number |
11440194
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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 | Gifu University |
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Principal Investigator |
KAWAMURA Takashi Gifu University, Faculty of Engineering, Professor, 工学部, 教授 (40026125)
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| Co-Investigator(Kenkyū-buntansha) |
EBIHARA Masahiro Gifu University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (80201961)
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| Project Period (FY) |
1999 – 2001
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥12,800,000 (Direct Cost: ¥12,800,000)
Fiscal Year 2001: ¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 2000: ¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 1999: ¥7,000,000 (Direct Cost: ¥7,000,000)
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| Keywords | group 9 element / cobalt / rhodium / iridium / dinuclear complex / electronic structure / X線結晶構造解析 / 電子構造 / 金属-金属間結合 / ホスフィン / アルシン / サイクリックボルタンメトリー / ESR / DFT計算 / クラスター錯体 / レドックス化学 / 触媒 / X線構造解析 / 金属原子間結合 / 水素添加 / 電子配置 / 密度汎関数法 |
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| Research Abstract |
This project explores the novel cluster compounds in which the frontier orbital in the group 9 metal framework delocalizes onto the ligands. We also aim to control the shape of the frontier orbital and the redox potential together.
( 1 ) Cobalt-rhodium mixed metal trinuclear clusters were synthesized. The redox potential of them indicated that the HOMO-LUMO gap of them were large in the rhodium rich clusters.
( 2 ) The cationic radical salt of [ Co_3Cp_3( μ_3-CPh )_2 ] was synthesized and determined its X-ray structure. Its HOMO was determined as outof-plane orbital which has appreciable electron density on the capping carbon atoms by using comparison of Xray data and ^1H-NMR paramagnetic shift.
( 3 ) Tricobalt clusters with halide-bridge [ Co_3Cp_3( μ_3-CPh )_2(μ-X ) ] were synthesized. The formation of the clusters were via oxidation of the intermediate which was constructed from the cation of the cobalt complex and halide ion.
( 4 ) Bis( μ-acetato ) dichlorodicarbonyldiiridium ( II ) complexes with group 15 compounds as the axial ligands, [ Ir_2( μ-O_2CMe )_2Cl_2( CO )_2L_2 ] ( L = PPh_3, PCy3 , P( OPh )_3, AsPh_3, SbPh_3 ) were synthesized. The Ir-Ir distances were longer than those of acetonitrile compounds. The complexes had a chemically reversible one-electron oxidation wave of which E1/2 values were 0.21 V for PCy3 complex. The ESR results indicatelhat their SOMO is the ^σIrIr orbital with ^σIrP^* or ^σIrAs^* character.
( 5 ) tetranuclear rhodium complex [ Rh_4( O_2CPr)_4Cl_4( CH_3CN )_4 ] catalyzed hydrogenation of olefin compounds.
( 6 ) A novel iridium( II ) dimer complexes with thiocarboxylato bridge were synthesized
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Report
(4 results)
Research Products
(10 results)
