用微电极和薄层循环伏安（ＣＶ）技术研究了Ｂｒ－对四苯基钴卟啉（（ＴＰＰ）Ｃｏ）在１，２＿二氯乙烷（ＤＣＥ）中电化学行为的影响．发现在较高电位下，两个Ｂｒ－轴向配位的（ＴＰＰ）Ｃｏ（ＩＩ）（Ｂｒ－）２其一个Ｂｒ－发生脱落表现出（ＴＰＰ）Ｃｏ（ＩＩ）（Ｂｒ－）的行为特征，这被证明是Ｂｒ－的氧化所致．证明了（ＴＰＰ）Ｃｏ（ＩＩ）（Ｂｒ－）在约０．１２Ｖ（ＳＣＥ）处还原，而（ＴＰＰ）Ｃｏ（ＩＩ）（Ｂｒ－）２则在大约Ｃｏ（Ｉ）／Ｃｏ（Ｉ）还原过程出现的更负的电位处发生还原
The effect of Br - anion on electrochemical behavior of (TPP)Co was investigated in 1,2 dichloroethane solution by microelectrode and thin layer cyclic voltammetry technique. It was found that the axially coordination of one Br - anion to (TPP)Co(Ⅲ)(Br -) 2 shifts the potential of porphyrin system to more positive value. The reduction peak of 0.12 V(vs.SCE) is attributed to the reduction of (TPP)Co(Ⅲ)(Br -). It is also postulated that the reduction of (TPP)Co(Ⅲ)(Br -) 2 occurred at a more negative potential where the reduction of the Co(Ⅱ)/Co(Ⅰ) process happened.
1TruxiloLA，DavisDG．Electrochemistryofcobalttetraphenylporphyrininaprotic．Media．Anal．Chem．，1975，47：22602KadishKM，BotomleyLA，BeroizD．Reactionsofpyridinewithaseriesofparasubstitutedtetraphenylporphyrincobaltandironcomplexes．Inorg．Chem．，1978，17：11243KadishKM，LinXQ，HanBC．Chlordebindingreactionsandelectrochemistryof（TPP）C″Oand（TPP）COClindichloromethane．Inorg．Chem．，1987，26：41614刘殿骏，林祥钦．OH－存在下四苯基卟啉合钴氧化过程的电化学和光谱电化学．化学学报，1994，52：235HuY，HanBC，BaoLYetal．Electrochemistryof（octaethylporphinato）cobalt（Ⅱ），（OEP）Co，underacarbonmonoxideatmosphere．electrogenerationandcharacterizationof［（OEP）Co（CO）］－．Inorg．Chem．，1991，30：24446严川伟．在线电化学／气相色谱与钴、镍卟啉的轴向配位和电催化机理研究：［博士学位论文］．长春：中国科学院长春应用化学研究所，19957严川伟，林祥钦．F－的轴向配位对（TPP）Co电化学氧化还原的影响研究．高等学校化学学报，1997，17：2208AdlerAD，LongoFR，KampasFetal．Onthepreparationofmetaloplrphyins．J．Inorg．Nucl．Chem．，1970，32：24439LinXQ，KadishKM．VacuumthinlayerspectroelectrochemicalcelwithadoubletPlatinumGauzeworkingelectrode．Anal．Chem．，1985，57：149810林祥钦，严川伟．中性配体存在下（OEP）Co的电化学和光谱电化学研究．化学学报，1997，55：52111SouzaFD，VilardA，CaemelbeckeEVetal．ElectrochemicalandspectroelectrochemicalbehaviorofCobalt（Ⅲ），Cobalt（Ⅱ）andCobalt（Ⅰ）complexesofmesotetraphenylporphinatebearingbromidesontheβpyrolepositions．Inorg．Chem．，1993，32：4042
