Orbital topology. II. Orbital mapping of unsymmetrical molecules. A survey of the thermal isomerizations of dewar isomers of isoelectronically substituted benzenes, cyclopentadienes, and cyclopentadienyl ions

✍ Scribed by Donald R. Kelsey

• Publisher: John Wiley and Sons
• Year: 1980
• Tongue: English
• Weight: 775 KB
• Volume: 1
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.540010103

✦ Synopsis

Abstract

Orbital mapping analysis, based on EHT and CNDO/2 semiempirical molecular orbitals, has been used to survey the thermal, disrotatory, ring‐opening isomerizations of bicyclo[2.2.0]hexa‐2,5‐dienes (Dewar benzenes), bicyclo[2.1.0]pent‐2‐enes, and bicyclo[2.1.0]pent‐2‐en‐5‐yl ions to their planar isomers. Results indicate that isoelectronic substitution (CH replaced by C^−^, O^+^, N, NH^+^, etc.) in the molecular framework may favor allowed thermal reactions in some cases, in contrast to the disallowed reaction predicted for the parent hydrocarbons.