Syntheses and properties of the polymethylenebis-(diphenylcyclopropenium) dications.

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概要

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• A series of polymethylenebis(diphenylcyclopropenium) dications with the polymethylene chain of one to six carbons (<B>4</B><SUB><I>n</I>=1–6</SUB>) were synthesized and characterized by spectral and analytical means. Among the dications <B>4</B><SUB><I>n</I>=3–6</SUB> which were isolated as perchlorates, <B>4</B><SUB><I>n</I>=3</SUB> was shown by the p<I>K</I><SUB>R<SUP>+</SUP></SUB> measurements to be destabilized by 1.3 p<I>K</I> units as compared with <B>4</B><SUB><I>n</I>=4–6</SUB>. The values of reduction potential exhibited the same tendency. The chromium(II) ion reduction of <B>4</B><SUB><I>n</I>=6</SUB>, a representative dication, afforded a polymeric material containing a hexylbenzene unit. The dication <B>4</B><SUB><I>n</I>=2</SUB> was isolable only as a complex salt with SbCl<SUB>6</SUB><SUP>−</SUP> and Cl<SUP>−</SUP>: the conventional hydride abstraction from 1,2-dicyclopropenylethane using trityl perchlorate resulted in rearrangements affording 4,9,10-triphenylphenanthrene and the unknown monocation C<SUB>32</SUB>H<SUB>25</SUB><SUP>+</SUP> containing the tropylium ring. A possible mechanism for these rearrangements is presented. On the other hand, the dication <B>4</B><SUB><I>n</I>=1</SUB> was observable only in a highly acidic solution due to the ready deprotonation yielding a new fully conjugated monocation <B>17</B>. This cation, characterized by remarkable stability (p<I>K</I><SUB>R<SUP>+</SUP></SUB> 8.9 in 50% aq acetonitrile), is formally represented as a triafulvene with a cyclopropenium ring substituted at the 4-position, but is shown to have a partially polarized electronic structure by <SUP>13</SUP>C NMR spectroscopy.

• 公益社団法人 日本化学会の論文

著者

• Komatsu Koichi

  Department Of Environmental And Biological Chemistry Fukui University Of Technology

• Okamoto Kunio

  Department of Fuel Chemistry Faculty of Engineering Kyoto University

• Waki Yoshinori

  Department of Hydrocarbon Chemistry, Faculty of Engineering, Kyoto University

• Masumoto Katsuhisa

  Department of Hydrocarbon Chemistry, Faculty of Engineering, Kyoto University

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