<紀要論文>
リチウムイオンによって加速されたクアドリシクランからノルボルナジエンへの原子価異性化反応

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概要 Thermally-forbidden reactions of quadricyclane to norbornadiene were accelerated by a catalytic amount of alkaline salts, where the presence of water and the nature of the counter anion and solvent af...fected the rate. Non-hydrated, highly electrophilic lithium ions obtained from Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (LiTFPB) promotes the valence-isomerization of quadricyclane to norbomadiene extremely; the relative rates in the presence of LiTFPB, LiTFPB・H_2O, and NaTFPB are 470:76:2.7 in CDCl_3 and 297:9.7:1 in C_6D_5CD_3. This is explained by the difference of the binding energy of lithium and sodium ion. The rates in CDCl_3 are higher than those in C_6D_5CD_3, which is supported by theoretical calculations.続きを見る

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登録日 2009.04.22
更新日 2017.06.07