Development of Novel Tetrapyrrole Ligands and Their Metal Complexes with New Functions

新型四吡咯配体及其新功能金属配合物的研制

• 批准号: 13440198
• 负责人: HISAEDA Yoshio
• 金额: $ 9.54万
• 依托单位: Kyushu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13440198/
• 关键词: pyrrole ligand; porphyrin; porphycene; corrin ring; hemiporphycene; crystal structure; myoglobin; modified electrode; コリン; コバルト錯体; 臭素化; トリフルオロメチル基; 軸配位平衡; コバルト-炭素結合; ポルフィリン異性体; 付加・酸化タンデム反応; 酸素化反応; 配位平衡; 有機金属錯体

Macrocyclic structure with tetrapyrrole skeleton is great interest because of its unique structure and function. In this study, porphycene and hemiporphycene which are structural isomers of porphyrin have been synthesized. Each structure was-determined by X-ray crystal analyses. These ligands complex with various transition metal, and especially substiution effect with macrocycle skeleton of its iron and cobalt complex was studied. The cobalt(II) complexes of a series of peripheral substituted porphycene ligands with bromine have been synthesized and its various properties have been investigated by means of CV,UV-VIS and NMR spectroscopies. Linear relationships between the number of bromine and various physicochemical properties were observed.Reconstituted myoglobin with iron porphycene as an artificial prosthetic group exhibits an extremely high molecular oxygen affinity and low autooxidation rate. This study showed that the modification of the heme framework will serve as an effective method for the creation of a unique functionalized hemoprotein.Hydrophobic vitamin B12 which is tetrapyrrole pigment was immobilized onto various electrode by a sol-gel reaction. The complex was physically retained in a silica gel film which is formed on an electrode. The immobilized complex exhibits the Co(II)/Co(I) redox couple and retain its electrochemical activity. This electroactive complex shows a high reactivity towards organic halides, and the controlled-potential electrolysis of benzyl bromide using the sol-gel modified electrode at -1.2 V vs. Ag/AgCl in aqueous solution afforded dehalogenated products, bibenzyl and toluene, with a total turnover number over 1000 for 1 hour.

具有四吡咯骨架的大环结构因其独特的结构和功能而备受关注。本研究合成了卟啉的结构异构体卟啉和半卟啉。每种结构均通过 X 射线晶体分析确定。研究了这些配体与多种过渡金属的络合情况，特别是对其铁钴络合物与大环骨架的取代作用进行了研究。合成了一系列外围取代卟啉配体与溴的钴(II)配合物，并通过CV、UV-VIS和NMR光谱研究了其各种性质。观察到溴的数量与各种理化性质之间存在线性关系。以铁烯为人工辅基的重构肌红蛋白表现出极高的分子氧亲和力和较低的自氧化率。本研究表明，血红素骨架的修饰将成为创建独特的功能化血红素蛋白的有效方法。疏水性维生素B12是四吡咯色素，通过溶胶-凝胶反应固定在各种电极上。该复合物被物理保留在电极上形成的硅胶膜中。固定化复合物表现出 Co(II)/Co(I) 氧化还原对并保留其电化学活性。该电活性配合物对有机卤化物表现出高反应活性，使用溶胶-凝胶修饰电极在-1.2 V vs. Ag/AgCl水溶液中对溴化苄进行控制电位电解，得到脱卤产物联苄和甲苯，1小时总转换数超过1000。

项目成果

H.Dejima, et al.: "New Myoglobin Reconstituted with an Iron Porphycene as a Structural Isomer of Heme Moiety"J.Inorg.Biochem. 86. 200-200 (2001)

H.Dejima 等人：“用铁卟啉作为血红素部分的结构异构体重构新肌红蛋白”J.Inorg.Biochem。

H.Shimakoshi et al.: "Formation and Cleavage of a Dicobalt Complex Bridged with a Pentamethylene Group"Chem.Lett.. 346-347 (2001)

H.Shimakoshi 等人：“与五亚甲基桥接的二钴络合物的形成和裂解”Chem.Lett.. 346-347 (2001)

H.Shimakoshi et al.: "Electroorganic Syntheses of Macrocyclic Lactones Mediated by Vitamin B_<12> Model Complexes"J.Electroanal.Chem.. Vol.507, No.1-2. 170-176 (2001)

H.Shimakoshi等人：“维生素B_12模型复合物介导的大环内酯的有机电合成”J.Electroanal.Chem..Vol.507，No.1-2。

T.Hayashi et al.: "Chemical Properties of Reconstituted Myoglobins with Functionalized Hemin Derivatives"J.Inorg.Biochem.. Vol.86, No.1. 57 (2001)

T.Hayashi 等人：“用功能化氯化血红素衍生物重建肌红蛋白的化学性质”J.Inorg.Biochem. 第 86 卷，第 1 期。

Y.Hisaeda et al.: "Reductive Molecular Transformations on Vitamin B_<12> Modified Electrodes"Mechanistic and Synthetic Aspects of Organic and Biological Electrochemistry. 109-112 (2003)

Y.Hisaeda等人：“维生素B_12修饰电极上的还原分子转化”有机和生物电化学的机理和合成方面。