单硝基四苯基卟啉合钴(Ⅱ)的电化学性质

Electrochemical Behaviour of Mono (nitro) Tetrabenzoporphyrin Cobalt( Ⅱ)

用循环伏安法和现场紫外－ 可见光谱研究了单硝基四苯基卟啉合钴（ Ⅱ） 的电化学性质，结果表明，在非水溶剂中其正电位区经历一步氧化过程，对应［（ Ｎ Ｏ２） Ｔ Ｐ Ｐ Ｃｏ（ Ⅲ）］ ＋ ／［（ Ｎ Ｏ２） Ｔ Ｐ Ｐ Ｃｏ（ Ⅱ）］ 的氧化反应，负电位区还原过程经历了［（ Ｎ Ｏ２） Ｔ Ｐ Ｐ Ｃｏ（ Ⅱ）］／π阴离子自由基和π阴离子自由基／［（ Ｎ Ｏ２） Ｔ Ｐ Ｐ Ｃｏ（ Ⅰ）］２ － 还原的两个步骤．阐述了溶剂的轴向配位对氧化还原电位的影响，指出吡咯环上吸电子基团（ － Ｎ Ｏ２） 的引入改变了还原过程的机理．

The electrochemical behaviour of Mono - (nitro) Tetrabenzoporphyrin Cobalt( Ⅱ) ,( N O2 ) T P P Co ( Ⅱ) , was studied by cyclic voltam metry and in situ U V - Vis spectroelec troche mistry in nonaqueous solutions . The results showed that the com pound undergoes one - stepoxidation on positive electropotential,corresponding to formation of [( N O2) T P P Co( Ⅲ)] + ,andtwostep reduction on negative electropotential,corresponding to formation of π- radical anion and[( N O2) T P P Co( Ⅰ)]2 - . It was expressed that axial - coordination of solvent affected the redoxelectropotential. The existence of drawing - electron group(nitro)on pyrrole ring changed the re duction mechanism .