ELECTRON-TRANSFER AND ION-PAIRING .29. MNDO CALCULATIONS AS A VALUABLE TOOL FOR STRUCTURE EVALUATION OF CONTACT ION-PAIRS

被引:18
作者
HAVLAS, Z [1 ]
NICK, S [1 ]
BOCK, H [1 ]
机构
[1] UNIV FRANKFURT,DEPT CHEM,NIEDERURSELER HANG,W-6000 FRANKFURT 50,GERMANY
关键词
D O I
10.1002/qua.560440406
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Contact ion pairs, essential intermediates of both chemical and biochemical reactions in solution, can be satisfactorily approximated by MNDO calculations as exemplified by the lithium and potassium salts of 2,5-trimethylsilyl-p-benzosemiquinone radical anion and by sodium tetraphenylallyl anion diethyl ether. Topics discussed are the structural changes of p-benzoquinone derivatives on single-electron reduction, the dynamics of the countercations in semiquinone radical contact ion pairs measured by temperature-dependent ESR spectra, as well as structural details of the sodium tetraphenyl-allylanion complex isolated such as its intramolecular Na dibenzene sandwich or its diethylether solvation.
引用
收藏
页码:449 / 467
页数:19
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