An Ab Initio Molecular Orbital Study of Isophosphinines

Abstract

Ab initio molecular orbital calculation at HF/6-31G*, HF/6-31G**, HF/6-311G**, HF/6-311++G**, RMP2-FC/6-31G*, and B3LYP/6-31G* levels of theory for geometry optimization and MP4(SDQ)/6-31G* for a single-point total energy calculation are reported for phosphinine and 13 isophosphinines 7-19 . Isomers 7-11 with an allenic system are calculated to be 8-18 kcal mol m 1 more stable than structures 12-17 with an acetylenic moiety. The calculated energy difference (66.19 kcal mol m 1 ) between phosphinine and the most stable isophosphinine (1-phospha-1,2,4-cyclohexatriene, 10 ) is smaller than the difference (78.96 kcal mol m 1 ) between benzene and the most stable isobenzene (cyclohexa-1,2,4-triene, 2 ). The isophosphinines 18 and 19 , with a butatriene moiety, are calculated to be the least stable isomers.