Source:http://linkedlifedata.com/resource/pubmed/id/15032547
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| Predicate | Object |
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| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
2
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| pubmed:dateCreated |
2004-3-22
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| pubmed:abstractText |
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)(F(X)R(Y) + R(X)F(Y)). The existence of the cross term (i.e., F(X)R(Y) and R(X)F(Y)) 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(X1, X2, ..., Xn) = Sigma(n-1)(i=1)Sigma(n)(j=i+1)k(ij)sigma(X)isigma(X)j.
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| pubmed:language |
eng
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| pubmed:journal | |
| pubmed:status |
PubMed-not-MEDLINE
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| pubmed:issn |
0095-2338
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| pubmed:author | |
| pubmed:issnType |
Print
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| pubmed:volume |
44
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| pubmed:owner |
NLM
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| pubmed:authorsComplete |
Y
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| pubmed:pagination |
652-7
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| pubmed:articleTitle |
Hammett equation and generalized Pauling's electronegativity equation.
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| pubmed:affiliation |
Department of Chemistry, University of Science and Technology of China, Hefei 230026, China. leiliu@chem.columbia.edu
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| pubmed:publicationType |
Journal Article
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