Syntheses and properties of the polymethylenebis-(diphenylcyclopropenium) dications.
Syntheses and properties of the polymethylenebis-(diphenylcyclopropenium) dications.
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聚亚甲基双(二苯基环丙烯鎓)二阳离子的合成和性质。
DOI：
10.1246/bcsj.55.2470
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发表时间：
1982
影响因子：
4
通讯作者：
K. Okamoto
中科院分区：
文献类型：
--
作者：
K. Komatsu;K. Masumoto;Yoshinori Waki;K. Okamoto
合成了一系列具有1 ~ 6个碳（4n= 1-6）链的聚亚甲基二（二苯基环丙烯）化合物，并用光谱和分析方法对其进行了表征。在被分离为高氯酸盐的4n=3 - 6的指示物中，pKR+测量表明，与4n= 4-6相比，4n=3被1.3个pK单位破坏。还原电位值也表现出相同的趋势。以铬离子还原4n=6为代表，得到了含有己基苯单元的聚合物材料。4n=2只能作为与SbCl6 -和Cl -的络合盐来分离：用高氯酸三酯从1,2-二环丙烯乙烷中传统的氢化物萃取得到重排，得到4,9,10-三苯基菲和未知的单位C32H25+，其中含有tropyum环。提出了这些重排的可能机制。另一方面，由于脱质子已准备好，仅在强酸性溶液中才观察到指示4n=1。
A series of polymethylenebis(diphenylcyclopropenium) dications with the polymethylene chain of one to six carbons (4n=1–6) were synthesized and characterized by spectral and analytical means. Among the dications 4n=3–6 which were isolated as perchlorates, 4n=3 was shown by the pKR+ measurements to be destabilized by 1.3 pK units as compared with 4n=4–6. The values of reduction potential exhibited the same tendency. The chromium(II) ion reduction of 4n=6, a representative dication, afforded a polymeric material containing a hexylbenzene unit. The dication 4n=2 was isolable only as a complex salt with SbCl6− and Cl−: the conventional hydride abstraction from 1,2-dicyclopropenylethane using trityl perchlorate resulted in rearrangements affording 4,9,10-triphenylphenanthrene and the unknown monocation C32H25+ containing the tropylium ring. A possible mechanism for these rearrangements is presented. On the other hand, the dication 4n=1 was observable only in a highly acidic solution due to the ready deprotonat...