title: Cooperative and competitive effects of substituents at C1 and C4 on the barriers to ring inversion of 5,5-difluorobicyclo[2.1.0]pentanes.
abstract: To identify the reasons for the very low barrier that has been measured for ring inversion of 1,4,5,5-tetrafluorobicyclo[2.1.0]pentane (deltaG(double dagger) = 6.8 +/- 0.2 kcal/mol), CASSCF and CASPT2 calculations have been performed on ring inversion in this and other bicyclo[2.1.0]pentanes. The results of the calculations show that a cooperative interaction between the geminal fluorines at C2 and the fluorines at C1 and C3 in the singlet cyclopentane-1,3-diyl transition structure (TS) contributes 3.7 kcal/mol to lowering the barrier to ring inversion in the tetrafluoro compound. In contrast, a competitive substituent effect in the TS for ring inversion of 1,4-dicyano-5,5-difluorobicyclo[2.1.0]pentane is predicted to raise the barrier height by 6.1 kcal/mol. The origin of these cooperative and competitive substituent effects is discussed.
authors.affiliation: Department of Chemistry, University of North Texas, Box 305070, Denton, Texas 76203-5070, USA.
authors.forename: G Robert
authors.initials: GR
authors.lastname: Shelton
authors.forename: David A
authors.initials: DA
authors.lastname: Hrovat
authors.forename: Weston Thatcher
authors.initials: WT
authors.lastname: Borden