Reaction of Heavy Transition Metal Cluster complexes-A Kinetic Approach

重过渡金属簇配合物的反应-动力学方法

• 批准号: 06044004
• 负责人: SASAKI Yoichi
• 金额: $ 4.16万
• 依托单位: HOKKAIDO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for international Scientific Research
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06044004/
• 关键词: Redox Reactions; Clluster Complexes; Oxided Bridge; Rhenium Complexes; Ruthenium Complexes; Kinetics; Electrochemistry; Hydroxo Bridge; 金属クラスター錯体; プロトン付加; 電気化学

This project was planned to study kinetics of redox reactions of oxobridged dinuclear complexes of heavy transition elements with special attention to the protonation at the oxide bridge associated with the redox processes. It was proposed to study with rhenium complexes, since they would take variety of oxidation states than any other elements. We have prepared number of new rhenium di (mu-oxo) complexes with different oxidation states, (III,IV) and (IV,IV), with ligands such as tris (2-pyridylmethyl) amine and its analogs, and studied their redox behavior electrochemically. Kinetic study of their redox reactions in aqueous media helped to understand the role of protonation at the oxide bridge on the reduction rate. However, the study in acetonitrile medium, which was proved to be a better solvent to study the protonation effect in electrochemical study, was suffered from some side reactions and did not provide expected information. Subsequently, we studied electrochemical and kinetic studies of proton-coupled redox reactions of related mononuclear oxorhenium (V) complexes which involve new complexes such as trans-[Re(O)(OH)(ethylenediamine)2]^<2+> and trans-[Re(O)2(imidazole)4]^+ prepared and structurally characterized in this study, and found necessary kinetic information on the redox reactions in aqueous and acetonitrile solution. In the latter solvent, proton-coupled redox behavior was studied by adding proton-donors with various pK_a values. Further kinetic study of the reduction of a ruthenium dimer, [Ru2(mu-O)(mu-CH3COO)2(bpy)2(Meim)2]^<2+>(bpy = 2,2'-bipyridine, Meim = 1-methylimidazole) gave some preliminary results on the effect of the protonation at the oxide bridge.

该项目计划研究重型过渡元件的氧化氧化物氧化还原反应的动力学，并特别注意与氧化还原过程相关的氧化物桥梁的质子化。提议使用rhenium络合物进行研究，因为它们会比其他任何元素都采用多种氧化态。我们已经准备了具有不同氧化态（III，IV）和（IV，IV）的新鼻rdi（Mu-oxo）复合物，并使用Tris（2-吡啶基甲基）胺及其类似物等配体进行了配体，并在电授权上研究了它们的Redox行为。对水性培养基中的氧化还原反应的动力学研究有助于了解质子化在氧化物桥上的作用在降低速率上。但是，在乙腈培养基中的研究被证明是在电化学研究中研究质子化效应的更好溶剂，但患有某些副反应，没有提供预期的信息。 Subsequently, we studied electrochemical and kinetic studies of proton-coupled redox reactions of related mononuclear oxorhenium (V) complexes which involve new complexes such as trans-[Re(O)(OH)(ethylenediamine)2]^<2+> and trans-[Re(O)2(imidazole)4]^+ prepared and structurally characterized in this study, and found necessary kinetic information on the redox水溶液和乙腈溶液中的反应。在后一种溶剂中，通过添加具有不同PK_A值的质子支持来研究质子耦合的氧化还原行为。进一步的动力学研究了唯一二聚体的还原，[Ru2（Mu-O）（Mu-Ch3Coo）2（BPY）2（MEIM）2]^<2+>（BPY = 2,2'-二吡啶，MEIM = 1-甲基咪唑）对蛋白质的蛋白质桥的影响产生了一些预选结果。

项目成果

Akihiro Ohto, Ayako Tokiwa-Yamamoto, Masaaki Abe, Tasuku Ito, Yoichi Sasaki, Keisuke Umakoshi, and Roderick D.Cannon: "Structure and Vibrational Spectra of Trinuclear Metal Cluster Complexes : a Question of Symmetry." Chem. Lett.97-98 (1995)

Akihiro Ohto、Ayako Tokiwa-Yamamoto、Masaaki Abe、Tasuku Ito、Yoichi Sasaki、Keisuke Umakoshi 和 Roderick D.Cannon：“三核金属簇配合物的结构和振动光谱：对称性问题。”

Takuya Takahira, Keisuke Umakoshi, Yoichi Sasaki: "Crystal Structure of Di-μ-oxo-bis(tris(2-pyridylmethyl)amine)rhenium(IV) Tetrakes(hexafluorophosphate),[Re_2(μ-0)_2(tpa)_2]・・・・・" Acta Crystallogr., Sect. C, Cryst. Struct. Commun.,. C51. 1870-72 (1994)

Takuy​​a Takahira、Keisuke Umakoshi、Yoichi Sasaki：“二-μ-氧代-双（三（2-吡啶甲基）胺）铼（IV）四（六氟磷酸盐）的晶体结构，[Re_2（μ-0）_2（tpa）_2 ]...” Acta Crystallogr.，C 部分，Cryst.Struct.Commun.,.C51.1870-72 (1994)

Ryoichi Hazama,Keisuke Umakoshi,Akio Ichimura,Yoichi Sasaki,et al.: "Dinuclear Oxomolybdenum (V) and Oxotungsten (V) Complexes of the Hexadentate Ligand N,N,N′N′-Tetrakis (2-pyridylmethyl) ethylenediamine……" Bull.Chem.Soc.Jpn.,. 68(2). 456-468 (1995)

Ryoichi Hazama、Keisuke Umakoshi、Akio Ichimura、Yoichi Sasaki 等人：“六齿配体 N,N,NN-四（2-吡啶甲基）乙二胺的双核氧钼 (V) 和氧钨 (V) 配合物.. ” Bull.Chem.Soc.Jpn.，68(2)。456-468 (1995)

Ryoichi Hazama, Keisuke Umakoshi, Akio Ichimura, Shinji Ikari, Yoichi Sasaki, and Tasuke Ito: "Dinuclear Oxomolybdenum (V) and Oxotungsten (V) Complexes of the Hexadentate Ligand N,N,N'N'-Tetrakis (2-pyridylmethy1) ethylenediamine and Its Propylenediamine

Ryoichi Hazama、Keisuke Umakoshi、Akio Ichimura、Shinji Ikari、Yoichi Sasaki 和 Tasuke Ito：“六齿配体 N,N,NN-四 (2-吡啶甲基1) 的双核氧钼 (V) 和氧钨 (V) 配合物

Takuya Takahira, Keisuke Umakoshi, Yoichi Sasaki: "Dinuclear Rhenium(III) Complexes with a Single Oxide Bridge,[Re_2(μ-0)Cl_2(L)2]_<2+> (L=2,2'-Bipy-ridine or 1,10-Phenanthoroline)." Chem. Lett.,. No.12. 2315-18 (1994)

Takuy​​a Takahira、Keisuke Umakoshi、Yoichi Sasaki：“具有单氧化物桥的双核铼 (III) 配合物，[Re_2(μ-0)Cl_2(L)2]_<2+> (L=2,2-Bipy-化学快报，2315-18（1994）。