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VOLTAMMETRIC STUDIES OF THE REDUCTION OF cis-AND trans-α-NITROSTILBENE

机译:顺式和反式-α-硝基苯乙烯还原的伏安研究

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摘要

The reduction of cis-α-nitrostilbene (cis-1) in acetonitrile occurs by initial formation of the radical anion followed by irreversible dimerization to give the dinitronate dianion, 3, of 1,4-dinitro-1,2,3,4-tetraphenylbutane, 2. The standard potential for the neutral/radical anion couple is -1.44 V vs. ferrocenium/ferrocene. The dimerization rate constant is 5.7 x 10~4 M~(-1)s~(-1) at 298 K and the dimerization equilibrium constant exceeds 10~6 M~(-1). The reduction of trans-α-nitrostilbene (trans-1) is extremely similar to that of cis-1 except for a marked deviation between simulation and experiment that occurs near the foot of the reduction peak. It is speculated that this deviation is caused by isomerization of the trans to the cis radical anions.
机译:乙腈中顺式-α-亚硝基苯乙烯(cis-1)的还原是通过最初形成自由基阴离子,然后发生不可逆的二聚作用而得到的1,4-二硝基-1,2,3,4-二亚硝酸根二价阴离子3。四苯基丁烷,2。中性/自由基阴离子对的标准电势为-1.44 V(对二茂铁/二茂铁)。在298 K下二聚化速率常数为5.7 x 10〜4 M〜(-1)s〜(-1),二聚平衡常数超过10〜6 M〜(-1)。反式-α-亚硝基二苯乙烯(trans-1)的还原与cis-1的还原极为相似,只是在还原峰附近的模拟与实验之间存在明显的偏差。据推测,该偏差是由反式异构化成顺式自由基阴离子引起的。

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