紀要論文 フェナイドアニオンの気相安定性に及ぼす置換基効果

中田, 和秀  ,  Nakata, Kazuhide Nakata  ,  藤尾, 瑞枝  ,  Fujio, Mizue  ,  都野, 雄甫  ,  Tsuno, Yuho

(29)  , pp.5 - 11 , 2015-04-01 , 法政大学情報メディア教育研究センター
ISSN:1882-7594
内容記述
環置換フェナイドアニオンの相対気相安定性を対応する無置換体とのプロトン移動平衡のエネルギー差として理論的に決定した。置換基効果は,誘起効果,共鳴効果,およびサチュレーション効果の三変数からなる拡張湯川−都野式によって精度良く相関された。相関結果から三変数からなる拡張湯川−都野式が論理的に妥当であることが証明された。
Relative gas-phase stabilities of ring-substituted phenide anions were theoretically determined utilizing proton transfer equilibria. The energies of respective species involved in the equilibria were calculated by DFT method. Obtained substituent effects were accurately analyzed by an extended Yukawa-Tsuno equation: –Δ EX =ρ(σ0 + r− ΔσR− + s ΔσS), which includes three terms of electronic effects. The r– value of 0.0 and the s value of 1.1 were obtained, showing the absence of the through-resonance and the significance of the saturation effect, respectively. This can be interpreted by the structure of phenide anion in which the anionic p-orbital is attached directly to the ipso position of the benzene ring but is orthogonal to the benzene π-electron system. The independent relation between the r– and s values in carbanionic systems revealed that two kinds of electronic effects quantified by the r– and s values are independent with each other showing adequacy of the extended Yukawa-Tsuno Eq.. Keywords : Substituent Effect, Phenide Anion, Extended Yukawa-Tsuno Equation, DFT Calculation
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http://repo.lib.hosei.ac.jp/bitstream/10114/11379/3/vol29_02.pdf

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