SUBSTITUENT EFFECTS ON THE REDOX REACTIONS OF PARA-SUBSTITUTED TETRAPHENYLPORPHYRIN COMPLEXES OF RUTHENIUM(II)
SUBSTITUENT EFFECTS ON THE REDOX REACTIONS OF PARA-SUBSTITUTED TETRAPHENYLPORPHYRIN COMPLEXES OF RUTHENIUM(II)
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DOI：
10.1021/ic00142a028
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发表时间：
1982-01-01
影响因子：
4.6
通讯作者：
KADISH, KM
中科院分区：
文献类型：
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作者：
MALINSKI, T;CHANG, D;KADISH, KM
研究了（（pX）TPP）Ru（CO）（Z-Bupy）在CH_2Cl_2 - 0.1TBAP溶液中的电化学氧化还原行为。研究了六种不同的络合物，其中X= Et 2N、OMe、Me、Pr、Cl和CP 3。除了（（p-Et 2N）TPP）Ru（CO）（Z-Bupy）有三次氧化和一次还原反应外，其它配合物都有两次氧化和一次还原反应。对于还原，λ/4与λ/4的曲线是线性的，而对于第一次和第二次氧化，是曲线的。然而，当用+代替取代基常数时，可以得到氧化的线性图。通过电子吸收、ESR和红外光谱研究了第一次控制电位氧化后产生的物种，并在此数据的基础上，将第一次氧化分配为在所有情况下以环为中心。与以前的结果与[（<$> X）TPP）Ru（CO）]+，室温ESR谱的[（（p-Et 2N）TPP）Ru（CO）（Z-Bupy）]+可以得到g= 2.016。提出了所有（（pX）TPP）Ru（CO）（Z-Bupy）配合物的氧化机理，并与以前发表的（（pX）TPP）Ru（CO）配合物在相同溶剂中的氧化机理进行了比较。
The electrochemical oxidation and reduction of ((pX) TPP) Ru (CO)(Z-Bupy) were investigated in CH2C12-0.1 TBAP solution. Six different complexes were investigated where X= Et2N, OMe, Me, Pr, Cl, and CP3. All of thecomplexes gave two oxidations and a single reduction process with the exception of ((p-Et2N) TPP) Ru (CO)(Z-Bupy), whichhad three oxidations and one reduction. Plots of ß vs. 4< r were linear for the reduction and curvilinear for the first and second oxidation. Linear plots could be obtained for oxidations, however, when+ was utilized in place of as the substituent constant. The species produced upon the first controlled-potential oxidation were investigated by electronic absorption, ESR, and infrared spectroscopy, and on the basis of this data, the first oxidation was assigned as ring centered in all cases. Unlike previous results with [(¿> X) TPP) Ru (CO)]+, a room-temperature ESR spectrum of [((p-Et2N) TPP) Ru (CO)(Z-Bupy)]+ could be obtained with g= 2.016. A mechanism for oxidation of all of the ((pX) TPP) Ru (CO)(Z-Bupy) complexes is presented, and comparisons are made with previously published data for ((pX) TPP) Ru (CO) complexes in the same solvent.