Synthesis of Nitrogen-containing Polymers Using Dinitrogen Splitting

二氮裂解合成含氮聚合物

• 批准号: 11650878
• 负责人: OYAIZU Kenichi
• 金额: $ 1.34万
• 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: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650878/
• 关键词: O_2 Reduction; N_2 Reduction; Multi-electron Transfer; Bond Order; Bridged Coordination; Electrochemical Raman Spectroscopy; MO Calculation; Vanadium Complex; 電極反応; 窒素還元; 窒素錯体; ジチオカルバマト; ニオブ錯体; アジン

The present research aims at making a catalytic system to allow molecular splitting of nitrogen for molecular conversion of organic molecules. One-step multi-electron transfer complexes were applied for the multi-electron reduction of nitrogen via a μ-dinitrido type complex.The four-electron reduction of oxygen catalyzed by a μ-oxo divanadium complex were expanded to the μ-dinitrido complex for the reduction of nitrogen. An effective complex, Nb diethyldithiocarbamate complex was found which formed the desired μ-dinitrido complex upon the reaction with nitrogen. Electrocatalytic reduction of nitrogen was established using the complex.The N-N bond splitting reaction was investigated using MO calculations and in-situ electrochemical Raman spectroscopy, which revealed that the multi-electron transfer is fostered by the catalytic system.

本研究的目的是建立一个催化体系，使分子分裂的氮分子转化的有机分子。将一步多电子转移配合物应用于氮的多电子还原反应，并将二钒配合物催化氧的四电子还原反应扩展到二氮配合物催化氮的还原反应。发现了一种有效的配合物--二乙基二硫代氨基甲酸铌配合物，它与氮气反应生成所需的μ-二氮配合物。利用分子轨道计算和原位电化学拉曼光谱研究了N-N键断裂反应，发现该催化体系促进了N-N键的多电子转移.

项目成果

K.Oyaizu,A.Haryono,J.Natori,H.Shinoda,E.Tsuchida: ""Electroreduction of μ-Oxo Iron (III) Porphyrins Adsorbed on an Electrode Leading to a Cofacial Geometry for the Iron (II) Complex : Unexpected Active Site for the Catalytic Reduction of O_2 to H_2O""Bull

K. Oyaizu、A. Haryono、J. Natori、H. Shinoda、E. Tsuchida：“吸附在电极上的 μ-Oxo 铁 (III) 卟啉的电还原导致铁 (II) 络合物的共面几何形状：出乎意料” O_2催化还原为H_2O的活性位点""Bull

K.Oyaizu,Y.Kumaki,K.Saito,E.Tsuchida: ""First Synthesis of High Molecular-weight Poly (2,6-difluoro-1,4-phenylene oxide) by Oxidative Polymerization""Macromolecules. 33. 5766-5769 (2000)

K.Oyaizu、Y.Kumaki、K.Saito、E.Tsuchida：“通过氧化聚合首次合成高分子量聚（2,6-二氟-1,4-苯醚）””大分子。

K.Oyaizu, T.Nakagawa, E.Tsuchida: ""Crystal Structures of Dimeric Manganese(III) Complexes of Tetradentate Schiff-base Ligands with Ancillary Axial Donors""Inorg.Chim.Acta. 305. 184-188 (2000)

K.Oyaizu、T.Nakakawa、E.Tsuchida：“四齿希夫碱配体与辅助轴向供体的二聚锰 (III) 配合物的晶体结构”“Inorg.Chim.Acta。

K.Oyaizu,K.Saito,E.Tsuchida: ""Copper-Catalyzed Oxidative Coupling of 2,4,6-Trimethylphenol with Oxygen""Chem.Lett.. 2000. 1318-1319 (2000)

K.Oyaizu、K.Saito、E.Tsuchida：“铜催化 2,4,6-三甲基苯酚与氧的氧化偶联”Chem.Lett.. 2000。1318-1319 (2000)

K.Oyaizu, K.Yamamoto, Y.Ishii, E.Tsuchida: ""Synthesis and Characterization of Nickel Dithiocarbamate Complexes Bearing Ferrocenyl Subunits""Chem.Eur.J. 5. 3193-3201 (1999)

K.Oyaizu、K.Yamamoto、Y.Ishii、E.Tsuchida：“带有二茂铁基亚基的二硫代氨基甲酸镍配合物的合成和表征”Chem.Eur.J。