Synthesis and electrochemistry of 2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetrakis (3,5-dichloro-2,6-dimethoxyphenyl)porphyrin (H2tdcdmpp), [CoII(tdcdmpp)] and [M(tdcdmpp)Cl](M = FeIII or MnIII)
Synthesis and electrochemistry of 2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetrakis (3,5-dichloro-2,6-dimethoxyphenyl)porphyrin (H2tdcdmpp), [CoII(tdcdmpp)] and [M(tdcdmpp)Cl](M = FeIII or MnIII)
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2,3,7,8,12,13,17,18-八氯-5,10,15,20-四(3,5-二氯-2,6-二甲氧基苯基)卟啉(H2tdcdmpp)的合成和电化学，[
DOI：
10.1039/dt9960002793
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发表时间：
1996
期刊：
影响因子：
--
通讯作者：
K. Kadish
中科院分区：
文献类型：
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作者：
M. Autret;Zhong;A. Antonini;T. Boschi;P. Tagliatesta;K. Kadish
合成了四种新的高氯代卟啉化合物：2，3，7，8，12，13，17，18-八氯-5，10，15，20-四（3，5-二氯-2，6-二甲氧基苯基）卟啉（H_2tdcdmpp），[Co Ⅱ（tdcdmpp）]和[M（tdcdmpp）Cl]（M = Fe Ⅲ或Mn Ⅲ）。通过氯化H2 tdmpp [5，10，15，20-四（2，6-二甲氧基苯基）卟啉]合成游离碱，并按照公开的方法进行金属化以得到配合物。同样的过渡金属衍生物的tdmpp也制备和所有8个合成的化合物进行了电化学研究，在苯甲腈或吡啶含有0.1摩尔dm-3 NBun 4 ClO 4。如所预期的，tdcdmpp络合物的半波电势向正值移动，而tdmpp物质的氧化或还原的半波电势与具有相同中心金属离子的四苯基卟啉（tpp）络合物的氧化或还原的E1/2相比负向移动。相对于tpp，还原的E1/2的阳极位移幅度是氯化卟啉报道的最大的，范围在590和860 mV之间，取决于具体的氧化还原反应和溶剂。对于相同化合物的氧化，观察到330-400 mV的较小ΔE 1/2，并且这些值可以与从平面M（tpp）到畸变M（obtpp）时E 1/2的可忽略的偏移进行比较。（obtpp = 2，3，7，8，12，13，17，18-八溴-5，10，15，20-四苯基卟啉）钴和铁的络合物，其中已知大环皱波效应优于添加的卤化物取代基的电子效应。这一结果表明，核心扭曲不能完全补偿Cl取代基的吸电子效应。大环畸变还引起UV/维斯吸收带的大的红移，并且对于氯化化合物相对于tdmpp络合物，λmax的这种移位范围高达40 nm。
Four new highly chlorinated porphyrins, 2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetrakis (3,5-dichloro-2,6-dimethoxyphenyl)porphyrin (H2tdcdmpp), [CoII(tdcdmpp)] and [M(tdcdmpp)Cl](M = FeIII or MnIII) have been prepared. The free base was synthesized by chlorination of H2tdmpp [5,10,15,20-tetrakis(2,6-dimethoxyphenyl)porphyrin] and metallated to give the complexes following published procedures. The same transition-metal derivatives of tdmpp were also prepared and all eight synthesized compounds were electrochemically investigated in benzonitrile or pyridine containing 0.1 mol dm–3 NBun4 ClO4. As expected the half-wave potentials of the tdcdmpp complexes are shifted towards positive values while those for oxidation or reduction of the tdmpp species are shifted negatively as compared with E½ for oxidation or reduction of tetraphenylporphyrin (tpp) complexes having the same central metal ions. The magnitude of the anodic shifts in E½ for reduction with respect to tpp is among the largest reported for chlorinated porphyrins and ranges between 590 and 860 mV depending upon the specific redox reaction and solvent. A smaller ΔE½ of 330–400 mV is seen for oxidation of the same compounds and these values can be compared to a negligible shift in E½ upon going from planar M(tpp) to distorted M(obtpp)(obtpp = 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinate) complexes of cobalt and iron where the effect of macrocycle ruffling is known to predominate over the electronic effects of added halide substituents. This result indicates that the core distortion cannot compensate totally for the electron-withdrawing effect of the Cl substituents. The macrocyclic distortion also induces a large red shift of the UV/VIS absorption bands and this shift in λmax ranges up to 40 nm for the chlorinated compounds with respect to the tdmpp complexes.