A Different Story of pi;-Delocalizations - The Distortivity of pi;-Electrons and Its Chemical Manifestations-[Shaik S , Shurki A , Danovich D ]化学.pdf

Chem. Rev. 2001, 101, 1501−1539 1501 A Different Story of -DelocalizationThe Distortivity of -Electrons and Its Chemical Manifestations† Sason Shaik,*,‡ Avital Shurki,‡ David Danovich,‡ and Philippe C. Hiberty*,§ Department of Organic Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University, 91904 Jerusalem, Israel, and Laboratoire de Chimie Physique, Groupe de Chimie The´orique, Universite´ de Paris-Sud, 91405 ORSAY Ce´dex, France Received August 28, 2000 Contents A. Bond Alternation in the Ground State of 1521 Substituted Benzene I. Introduction 1502 1. Modes of Bond Alternation Induced by 1521 II. Background on -Delocalization and 1503 Strain and -Electron Count -Distortivity B. -Strain and How It Causes -Distortivity to 1522 A. Pre-electron Notions of -Delocalization 1503 Manifest B. Quantum Chemical Notion of -Delocalization 1504 1. Origins of Bond Alternation of the 1522 C. -Distortivity in Hu¨ckel-Type Theories 1506 -Frame III. -DistortivityA Conclusion from a Broad 1506