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Progress in Chemistry 2007, Vol. 19 Issue (9): 1239-1248 Previous Articles   Next Articles

• Invited Article •

π-σ Energy Partition and Geometry Optimization under the Restrictions of π-Orbital Interactions

Yu Zhongheng** Bao Peng   

  1. Beijing National Laboratory for Molecular Sciences , State Key Laboratory for Structural Chemistry of Unstable & Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China
  • Received: Revised: Online: Published:
  • Contact: Yu Zhongheng
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The history of energy partition is reviewed.It is emphasized that the energy partition is to provide quantum calculation with the chemical meanings. The new methods of energy partition and geometry optimization under restrictions of orbital interactions are introduced, and these are developed in our research group. Based on these two methods, the viewpoint that π- electron delocalization is destabilization have been brought forward.the fundamental causality of classical organic structure theory, a relationship between resonance and molecular conformation, seems to be overturns, and it is confirmed that π-π and σ-σ orbital interactions are the driving forces for distorting NBA away from its planar geometry.A new quantitative method for evaluating aromaticity energy is developed, indicating that the reference molecule (or molecules) is no longer necessary for calculating stabilizing enenrgy for aromatic molecule.The roles of electrostatic and electron delocalization in forming chemical bond are distinguished quantitatively.Substitutent effects and driving forces for distorting strained cyclic molecules are discussied.
Key words: energy partition, restrictions of orbital interactions, geometry optimization, electron delocalization, aromaticity, substituent effect, cyclic strain

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[ 1 ] Libit J , Hoffmann R. J . Am. Chem. Soc. , 1974 , 96 : 1370 —1383
[ 2 ] Epiotis N D. J . Am. Chem. Soc. , 1973 , 95 : 3087 —3096
[ 3 ] Coulson C A , Longuet-Higgin H C. Proc. Roy. Soc. Ser. A ,1947 , 191 : 39 —39
[ 4 ] Dewar M J S , Dougherty R C. The PMO Theory of Organic Chemistry. NY: Plenum Press , 1975
[ 5 ] SalemL. J . Am. Chem. Soc. , 1968 , 90 : 543 —552
[ 6 ] Epiotis N D , Cherry W R , Shaik S , et al . Topics in Current Chemistry , Vol . 70. NY: Springer , 1977
[ 7 ] Epiotis N D. Lecture Notes in Chemistry , Vol . 34. NY: Springer Verlag , 1983
[ 8 ] Epiotis N D. Deciphering the Chemical Code. NY: VCH Publishers , 1996
[ 9 ] Houk K N. Acc. Chem. Res. , 1975 , 8 : 361 —369
[10] Woodward R B , Hoffmann R. The Conservation of Orbital Symmetry. NY: Academic Press Inc. , 1970
[11] Fleming I. Frontier Orbitats and Organic Chemistry. NY: Wiley Interscience , 1976
[12] Mulliken R S , Parr R G. J . Chem. Phys. , 1951 , 19 : 1271 —1278
[13] Kollmar H. J . Am. Chem. Soc. , 1979 , 101 : 4832 —4840
[14] Kitaura K, Morokuma K. Int . J . Quantum Chem. , 1976 , 10 :325 —340
[15] Jug K, Hiberty P C , Shaik S. Chem. Rev. , 2001 , 101 : 1477 —1500
[16] Glendening E D , Badenhoop J K, Reed A E , et al . NBO 510.Madison : Theoretical Chemistry Institute , University of Wisconsin ,2001
[17] Jordan K D , Paddon-Row M N. Chem. Rev. , 1992 , 92 : 395 —410
[18] Paddon-Row M N. Acc. Chem. Res. , 1982 , 15 : 245 —251
[19] Yu Z H , Li L T , Fu W, et al . J . Phys. Chem. A , 1998 , 102 :2016 —2028
[20] Yu Z H , Xuan Z Q , Wang T X, et al . J . Phys. Chem. A ,2000 , 104 : 1736 —1747
[21] Yu Z H , Peng X Q. J . Phys. Chem. A , 2001 , 105 : 8541 —8553
[22] Yu Z H , Xuan Z Q. J . Mol . Struct . (Theochem) , 1999 , 488 :101 —112
[23] Yu Z H. Computers Chem. , 1994 , 18 : 95 —102
[24] Bao P , Yu Z H. J . Comput . Chem. , 2006 , 27 : 809 —824
[25] Burgi H B , Dunitz J D. Helv. Chim. Acta , 1971 , 54 : 1255 —1260
[26] Xu H , Yu Z H. J . Mol . Struct . (Theochem) , 2004 , 682 : 37 —46
[27] Streitweiser A , Heathcock C H. Introduction to Organic Chemistry. NY: Macmillan , 1985
[28] Neckers D , Doyle M P. Organic Chemistry. NY: John Wiley ,1977
[29] Liu X W, Bao P , Ma Y P , et al . J . Mol . Struct . (Theochem) ,2005 , 729 : 1985 —1911
[30] 刘向文(Liu X W) , 包鹏(Bao P) , 虞忠衡(Yu Z H) . 高等学校化学学报(Chem. J . Chin. Univ. ) , 2006 , 27 : 96 —99
[31] Katritzky A R , Barczynski P , Musumarra G, et al . J . Am.Chem. Soc. , 1989 , 111 : 7 —15
[32] Krygowski T M. J . Chem. Inf . Comput . Sci . , 1993 , 33 : 70 —78
[33] Krygowski T M, Cyrański M. Tetrahedron , 1996 , 52 : 1713 —1722
[34] Krygowski T M, Cyrański M. Tetrahedron , 1996 , 52 : 10255 —10264
[35] Corminboeuf C , Heine T , Seifert G, et al . Phys. Chem. Chem.Phys. , 2004 , 6 : 273 —276
[36] Schleyer P V , Maerker C , Dransfeld A , et al . J . Am. Chem.Soc. , 1996 , 118 : 6317 —6318
[37] Poater J , Fradera X, Duran M, et al . Chem. Eur. J . , 2003 , 9 :400 —406
[38] Poater J , Fradera X, Duran M, et al . Chem. Eur. J . , 2003 , 9 :1113 —1122
[39] Bultinck P , Ponec R , Damme S V. J . Phys. Org. Chem. ,2005 , 18 : 706 —718
[40] Bultinck P , Rafat M, Ponec R , et al . J . Phys. Chem. A , 2006 ,110 : 7642 —7648
[41] Streitwieser A. Molecular Orbital Theory for Organic Chemists.NY: Wiley , 1961
[42] Schaad L J , Hess B A. Chem. Rev. , 2001 , 101 : 1465 —1476
[43] Hess B A , Schaad L J . J . Am. Chem. Soc. , 1971 , 93 : 305 —310
[44] Schleyer P V , Puhlhofer F. Org. Lett . , 2002 , 4 : 2873 —2876
[45] Cyrański M K. Chem. Rev. , 2005 , 105 : 3773 —3811
[46] Kistiakowsky G B , Ruhoff J R , Smith H A , et al . J . Am. Chem.Soc. , 1936 , 58 : 146 —153
[47] Mo Y R , Schleyer P V. Chem. Eur. J . , 2006 , 12 : 2009 —2020
[48] Bao P , Yu Z H. J . Phys. Chem. A , 2007 , 111 (24) : 5304 —5313
[49] The supporting materials for Bao P , Yu Z H. J . Phys. Chem. A ,2007 , 111 (24) : 5304 —5313
[50] Bird C W. Tetrahedron , 1997 , 53 : 13111 —13118
[51] Bird C W. Tetrahedron , 1997 , 53 : 3319 —3324
[52] Bird C W. Tetrahedron , 1996 , 52 : 9945 —9952
[53] Wiberg KB , Nakaji D , Breneman C M. J . Am. Chem. Soc. ,1989 , 111 : 4178 —4190
[54] Cyrański M K, Krygowski T M, Katritzky A R , et al . J . Org.Chem. , 2002 , 67 : 1333 —1338
[55] Lewis G N. Valence and Structure of Atoms and Molecules. NY:The Chemical Catalogue Company , 1923
[56] Murrel J N , Kettle S F , Tedder J M. The Chemical Bond. NY:John Willey &Sons , 1978
[57] Mills W H , Nixon I G. J . Chem. Soc. , 1930 , 2510 —2511
[58] Stanger A. J . Am. Chem. Soc. , 1998 , 120 : 12034 —12040
[59] Shaik S , Shurki A , Danovich D , et al . Chem. Rev. , 2001 ,101 : 1501 —1540
[60] Diercks R , Vollhardt K P C. J . Am. Chem. Soc. , 1986 , 108 :3150 —3152
[61] Toda F , Ganaft P. Chem. Rev. , l992 , 92 : 1685 —1707
[62] Baldridge K K, Siegel J . J . Am. Chem. Soc. , 1992 , 114 :9583 —9587
[63] Stanger A , Ashkenazi N , Boese R. J . Org. Chem. , 1998 , 63 :247 —253
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