Orbital interactions and solvent effects determining the stability of condensed cyclopentadienides in solution

Kazunari Yoshizawa, Kazuyuki Yahara, Aya Taniguchi, Tokio Yamabe, Tomomi Kinoshita, Ken'ichi Takeuchi

Research output: Contribution to journalArticlepeer-review

8 Citations (Scopus)


The structure and the stability of various cyclopentadienides, which involve 6π, 10π, 14π, and 22π electrons, are investigated from computations at various levels of theory as well as from orbital interaction analyses. The reason that some of the cyclopentadienides are stabilized and others are destabilized by the introduction of aromatic rings is discussed in terms of absolute hardness and orbital interaction. Cyclopentadienide, a special 6π-electron system, has the largest value of absolute hardness among the condensed cyclopentadienides investigated; thus this carbanion resists both oxidation and reduction most strongly. The absolute hardness decreases when aromatic rings are introduced to cyclopentadienide to form condensed cyclopentadienides, depending on the way they are connected. Computed values of the ionization potential and oxidation potentials measured in solution have a linear correlation within isomers of the same size, but are not in agreement for different sets of isomers. Solvent effects on the ionization potential are assessed by performing self-consistent reaction field calculations, the results being in excellent agreement with experiments. It is demonstrated that the solvent effects are significant in small cyclopentadienides of 6π- and 10π-electron systems, compared to larger ones and that addition of condensed aromatic rings intrinsically stabilizes the formed condensed cyclopentadienides with respect to ionization potential.

Original languageEnglish
Pages (from-to)2821-2829
Number of pages9
JournalJournal of Organic Chemistry
Issue number8
Publication statusPublished - Apr 16 1999
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Organic Chemistry


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