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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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Mendeley出力
KJ00004507971