Hammett equation and generalized Pauling's electronegativity equation

被引:82
作者
Liu, L [1 ]
Fu, Y [1 ]
Liu, R [1 ]
Li, RQ [1 ]
Guo, QX [1 ]
机构
[1] Univ Sci & Technol China, Dept Chem, Hefei 230026, Peoples R China
来源
JOURNAL OF CHEMICAL INFORMATION AND COMPUTER SCIENCES | 2004年 / 44卷 / 02期
关键词
D O I
10.1021/ci0342122
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Substituent interaction energy (SIE) was defined as the energy change of the isodesmic reaction X-spacer-Y + H-spacer-H --> X-spacer-H + H-spacer-Y. It was found that this SIE followed a simple equation, SIE(X,Y) = -ksigma(X)sigma(Y), where k was a constant dependent on the system and sigma was a certain scale of electronic substituent constant. It was demonstrated that the equation was applicable to disubstituted bicyclo [2.2.2] octanes, benzenes, ethylenes, butadienes, and hexatrienes. It was also demonstrated that Hammett's equation was a derivative form of the above equation. Furthermore, it was found that when spacer = nil the above equation was mathematically the same as Pauling's electronegativity equation. Thus it was shown that Hammett's equation was a derivative form of the generalized Pauling's electronegativity equation and that a generalized Pauling's electronegativity equation could be utilized for diverse X-spacer-Y systems. In addition, the total electronic substituent effects were successfully separated into field/inductive and resonance effects in the equation SIE(X,Y) = -k(1)F(X)F(Y) - k(2)R(X)R(Y) - k(3)(FXRY + RXFY). The existence of the cross term (i.e., FXRY and RXFY) suggested that the field/inductive effect was not orthogonal to the resonance effect because the field/inductive effect from one substituent interacted with the resonance effect from the other. Further studies on multi-substituted systems suggested that the electronic substituent effects should be pairwise and additive. Hence, the SIE in a multi-substituted system could be described using the equation SIE(X-1, X-2,..,X-n) = -Sigma(i=1)(n-1)Sigma(j=i+1)(n)k(ij)sigma(Xi)sigma(Xj).
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页码:652 / 657
页数:6
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