Molecular Conversion Using One-Step Multi-electron Transfer Complex

使用一步多电子转移复合物进行分子转换

• 批准号: 07651006
• 负责人: YAMAMOTO Kimihisa
• 金额: $ 1.41万
• 依托单位: Waseda University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07651006/
• 关键词: Vanadium Complex; Multi-nuclear Complex; O_24-electron Reduction; X-ray Analysis; mu-Dioxo Complex; One-step Multi-electron Transfer; Electrode Reaction; Planer Ligand; 複核錯体; 酸素還元

Vanadyl (salen) multi-nuclear complexes act as electron mediators to allow catalytic multi-electron electroeduction of oxygen. By adjusting redox potentials to the value close to the thermodynamic potential for the 4-electron reduction of oxygen using a variety of ligands, the objective of the present study is to establish multi-electron reduction systems of molecular oxygen by the use of these complexes as electron mediators. It is also intended to elucidate novel molecular conversion systems by the use of these complexes as oxidation systems for organic substrates.It the first year, vanadium complexes with inert ligands were prepared and the redox potentials were determined. Also, the corresponding dinuclear complexes were prepared. X-ray studies of these complexes revealed the structure of the oxygen-binding sites in these complexes. By near-infrared spectrum, the redox state of the complexes were determined. Kinetic analysis for the oxygenation of the catalyst revealed the presence of mu-dioxo intermediate.In the second year, the selected vanadium complexes were used as electron mediators, and the reduction of oxygen was examined. Koutecky-Levich Plots obtained by the rotating ring-disk voltammetry revealed the 4-electron process and the production of water. The turn-over number of the catalyst was determined to exceed 10. It was concluded that selective 4-electron reduction system of oxygen was established.

钒（salen）多核配合物作为电子介质，允许催化多电子电析出氧。通过调节氧化还原电位的值接近的热力学势的4-电子还原的氧使用各种配体，本研究的目的是建立多电子还原系统的分子氧使用这些配合物作为电子介体。第一年，我们制备了含惰性配体的钒配合物，并测定了它们的氧化还原电位。并制备了相应的双核配合物。这些复合物的X射线研究揭示了这些复合物中的氧结合位点的结构。通过近红外光谱测定了配合物的氧化还原状态。催化剂氧化反应动力学分析表明存在μ-二氧代中间体。第二年，选择钒配合物作为电子媒介物，考察了氧的还原反应。通过旋转环盘伏安法得到的Koutecky-Levich图揭示了4电子过程和水的产生。测定催化剂的转化数超过10。建立了氧的选择性四电子还原体系。

项目成果

K.Yamamoto,S.Kobayashi,E.Shouji,E.Tsuchida: "Oxidative Coupling of Methyl Phenyl Sulfide Via Sulfonium Formation Usong a Oxovanadium Complex" J. Org. Chem.(in press).

K.Yamamoto，S.Kobayashi，E.Shouji，E.Tsuchida：“使用氧钒络合物通过形成锍来氧化甲基苯硫醚”J. Org。

K.Yamamoto,K.Oyaizu,and E.Tsuchida: "Catalytic Cycle of a Divanadium Complex with Salen Ligands in O_2 Reduction : Two-Electron Redox Process of the Dinuclear Center" J Am. Chem. Soc.118. 12665-12672 (1996)

K.Yamamoto、K.Oyaizu 和 E.Tsuchida：“O_2 还原中具有 Salen 配体的二钒配合物的催化循环：双核中心的双电子氧化还原过程”J Am。

K.Oyaizu, K.Yamamoto, K.Yoneda, and E.Tsuchida: "Multielectron Redox Process of Vanadium Complexes in Oxidation of Low-Coordinate Vanadium (III) to Oxovanadium (V) with Dioxygen" Inorg.Chem.35. 6634-6635 (1996)

K.Oyaizu、K.Yamamoto、K.Yoneda 和 E.Tsuchida：“用双氧将低配位钒 (III) 氧化为氧化钒 (V) 时钒络合物的多电子氧化还原过程”Inorg.Chem.35。

K.Oyaizu,K.Yamamoto,K.Yoneda,and E.Tsuchida: "Multielectron Redox Process of Vanadium Complexes in Oxidation of Low-Coordinate Vanadium (III) to Oxovanadium (V) with Dioxygen" Inorg. Chem. 35. 6634-6635 (1996)

K.Oyaizu、K.Yamamoto、K.Yoneda 和 E.Tsuchida：“用双氧将低配位钒 (III) 氧化为氧钒 (V) 时钒配合物的多电子氧化还原过程”Inorg。

K.Yamamoto, K.Oyaizu, and E.Tsuchida: "Catalytic Cycle of a Divanadium Complex with Salen Ligands in O_2 Reduction : Two-Electron Redox Process of the Dinuclear Center" J Am.Chem.Soc.118. 12665-12672 (1996)

K.Yamamoto、K.Oyaizu 和 E.Tsuchida：“O_2 还原中具有 Salen 配体的二钒配合物的催化循环：双核中心的双电子氧化还原过程”J Am.Chem.Soc.118。