A novel energy partition for gaining new insight into the fundamental principles of organic chemistry
Yu, ZH
AbstractOur researches, supported by the National Natural Science Foundation of China, on the fundamental theories of organic chemistry are reviewed. A new method for ab initio energy partition is being developed in order to gain new insight into the nature of electron delocalization, and it is able to provide any molecule with a fragment MO basis set in which the pi and sigma systems have been separated out no matter whether molecule is planar or nonplanar as well as whether the pi system is conjugated or cumulated. Contrary to the HMO theory, the pi electron delocalization has a great influence upon the original pi systems themselves as well as upon the sigma framework due to the pi-sigma space interaction. Accordingly, aromatic compounds can be divided into three groups and a delocalized pi system itself is always destabilized, the dependence of aromatic ring current upon the CT was reveled, and ring rigidity has been defined as a new aromatic index. Based on the distinction between the CT and EX delocalizations, it was found that the stabilizing CT interaction is practically destabilization and the destabilizing EX interaction is stabilization as far as their effects on the behaviors of whole molecule are concerned. Consequently, the conclusions that the pi-pi, pi-sigma and non-bonded sigma-sigma interaction are always destabilization in the case of stilbene-like species are reasonable. Out of the classical expectation, the pi-pi interaction has only a slight effect on molecular behaviors. Particularly, it is the a-a destabilization interaction, rather than nuclear repulsion as classically thought, to distort molecule away from its planar geometry, and stilbene-like species may exist preferentially in a "crowded" geometry. The roles of the pi and sigma electrons in determining molecular behaviors should be reevaluated.
KeywordElectron Delocalization Structure Theory Of Organic Chemistry a New Method For Energy Partition Ct And Ex Delocalization Aromaticity Conformation
Indexed BySCI
WOS IDWOS:000173075900022
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Document Type期刊论文
Corresponding AuthorYu, ZH
AffiliationChinese Acad Sci, Inst Chem, State Key Lab Struct Chem & Unstable & Stable Spe, Beijing 10080, Peoples R China
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Yu, ZH. A novel energy partition for gaining new insight into the fundamental principles of organic chemistry[J]. CHINESE JOURNAL OF ORGANIC CHEMISTRY,2001,21(11):949-953.
APA Yu, ZH.(2001).A novel energy partition for gaining new insight into the fundamental principles of organic chemistry.CHINESE JOURNAL OF ORGANIC CHEMISTRY,21(11),949-953.
MLA Yu, ZH."A novel energy partition for gaining new insight into the fundamental principles of organic chemistry".CHINESE JOURNAL OF ORGANIC CHEMISTRY 21.11(2001):949-953.
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