Synthesis and Electronic Structure of Group 9 Metal Clusters with Novel Framework

新型骨架9族金属团簇的合成及电子结构

• 批准号: 11440194
• 负责人: KAWAMURA Takashi
• 金额: $ 8.19万
• 依托单位: Gifu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11440194/
• 关键词: 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

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

这个项目探索了9族金属骨架中的前线轨道离域到配体上的新型簇合物。我们的目标是同时控制前线轨道的形状和氧化还原电势。(1)合成了钴-铑混合金属三核簇合物。它们的氧化还原电位表明它们在富Rh簇合物中具有较大的HOMO-LUMO能隙。(2)合成了阳离子自由基盐[Co_3Cp_3(μ_3-CPH)_2]，并测定了其X-射线结构。通过X-射线衍射数据和1H-核磁共振顺磁位移的比较，确定其HOMO为离面轨道。(3)合成了具有卤代桥结构的三钴簇合物[Co_3Cp_3(μ_3-CPH)_2(μ-X)]。(4)以15族化合物为轴向配体合成了双(μ-乙酰)二氯二羰基二铱(II)配合物[Ir_2(μ-O_2CMe)_2Cl2(CO)_2L_2](L=PPh3，PCy3，P(OPh)3，AsPh_3，SbPh_3)。红外-红外光谱距离比乙腈化合物的红外光谱距离长。络合物有一个可逆单电子氧化波，其中PCy3络合物的E_1/2为0.21V。电子自旋共振结果表明，它们的自组态是具有^σirp^*或^σirr^*性质的^σirIr轨道。(5)四核铑配合物[Rh_4(O_2CPr)_4Cl4(CH_3CN)_4]催化烯烃类化合物的氢化。(6)合成了一种新的含硫代羧基桥联的Ir(II)二聚体配合物。

项目成果

Z.Yang 他3名: "Homogeneous Hydrogenation of Olefins Catalyzed by a Novel Tetrarhodium(II) Complex as Precursor in Aqueous Solution"J.Mol.Cat.,A. 158・2. 509-514 (2000)

Z. Yang等3人：“新型四铑(II)配合物在水溶液中催化烯烃的均相氢化”J. Mol., A. 158・2 (2000)。

Kanematsu,Naohiro, et al.: "A one-step synthesis of an Ir( II ) dinuclear complex. Preparation, structures and properties of bis ( μ-acetato ) dichlorodicarbonyl-diiridium( II ) complexes"J. Chem. Soc., Dalton Trams.. 4413-4417 (1999)

Kanematsu、Naohiro 等人：“Ir( II) 双核络合物的一步合成。双 (μ-乙酸) 二氯二羰基-二铱 (II) 络合物的制备、结构和性质”J. Chem.，道尔顿电车.. 4413-4417 (1999)

N.Kanematsu, M.Ebihara, T.Kawamura: "A one-step synthesis of an Ir (II)dinuclear complex. Preparation, structures and properties of bis( -acetato)dichlorodicarbonyl-diiridium(II) complexes"J. Chem. Soc., Dalton Trams. 4413-4417 (1999)

N.Kanematsu、M.Ebihara、T.Kawamura：“Ir(II)双核配合物的一步合成。双(-乙酰基)二氯二羰基-二铱(II)配合物的制备、结构和性质”J。

兼松直弘、海老原昌弘、川村尚: "A one-step synthesis of an Ir(II) dinuclear complex. Preparation, structures and properties of bis (μ-acetato) dichlorodicarbonyldiiridium(II) complexes"J. Chem., Soc., Dalton Trans.,. 4413-4417 (1999)

Naohiro Kanematsu、Masahiro Ebihara、Hisashi Kawamura：“Ir(II) 双核配合物的一步合成。双 (μ-乙酰) 二氯二羰基二铱 (II) 配合物的制备、结构和性质” J. Chem., Soc.,道尔顿翻译，4413-4417（1999）

Z.Yang, M.Ebihara, T.Kawamura: "Homogeneous hydrogenation of olefins catalyzed by a novel tetrarhodiumII) complex as precursor in aqueous solution"J. Mol. Catal., A. 158. 509-514 (2000)

Z.Yang，M.Ebihara，T.Kawamura：“新型四铑II)络合物作为水溶液中的前体催化烯烃的均相氢化”J。