Properties of Radical Anions of Triptindanones and Indanones: Electronic Communication and Stability of Ion Pairs Containing Lithium Cations
Properties of Radical Anions of Triptindanones and Indanones: Electronic Communication and Stability of Ion Pairs Containing Lithium Cations
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曲丁丹酮和茚满酮自由基阴离子的性质：电子通讯和含有锂阳离子的离子对的稳定性
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发表时间：
2009
期刊：
影响因子：
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通讯作者：
D. Kuck
中科院分区：
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作者：
J. Jaworski;Agnieszka Kosson;S. Filipek;M. Koliński;D. Kuck
采用电化学方法研究了3种相关空间酮9-雷公藤丹酮（T1）、9,10-雷公藤丹二酮（T2）和9,10,11-雷公藤丹三酮（T3）在含四烷基铵和锂离子的DMF溶液中的阴离子和自由基性质，并与平面1-茚酮（I1）、1,3-茚二酮（I2）和1,2,3-茚三酮（I3）的阴离子性质进行了比较。发现T2中四乙基和四丁基阳离子存在时羰基之间的电子通信比I3小两倍，但在Li+存在时通信大大减少。与Li+离子形成离子对的自由基阴离子T1•−、T2•−和离子T22−的缔合常数Kass分别为493±38、418±32和（2.6±0.9）× 107 dm3 mol−1。最后一个离子对的螯合结构得到了负电荷分布的理论计算的支持。log Kass与最大值之间的线性关系。
The properties of radical anions and dianions of three related spatial ketones, 9-triptindanone (T1), 9,10-triptindanedione (T2), and 9,10,11-triptindanetrione (T3), in DMF solutions containing tetraalkylammonium and lithium cations were investigated by electrochemical methods and compared with the properties of radical anions of planar 1-indanone (I1), 1,3-indanedione (I2), and 1,2,3-indanetrione (I3). Electronic communication between carbonyl groups in T2 in the presence of tetraethyl and tetrabutyl cations was found to be two times smaller than for I3, but communication decreases substantially in the presence of Li+. Radical anions T1•− and T2•− and dianion T22− that form ion pairs with Li+ cations and corresponding association constants Kass are equal to 493 ± 38, 418 ± 32 and (2.6 ± 0.9) × 107 dm3 mol−1, respectively. The chelating structure of the last ion pair is supported by theoretical calculations of the distribution of the negative charge. A linear relationship between log Kass and maximum valu...