Stereochemical interactions in ammonium dications, hypervalent diammonium cation-radicals and ammonium radicals. A B3-MP2 computational study

Hypervalent ammonium radicals and cation-radicals derived from cis and trans-cyclopentane-1,2-diamine have been studied computationally with the goal of elucidating intramolecular interactions between the ammonium and amine functional groups in a conformationally rigid model system. Hypervalent cis and trans-cyclopentane-1-ammonium-2-amine radicals are only marginally stable against dissociation by loss of an ammonium hydrogen atom and ammonia. The radicals are predicted to exhibit very similar dissociations originating from the ground and excited electronic states. The dissociation and transition state energies in bifunctional hypervalent ammonium radicals are analogous to those reported previously for monofunctional ammonium radicals. Stereochemical effects are predicted to occur in the formation and dissociations of hypervalent cis and trans-cyclopentane-1,2-diammonium cation-radicals. The cis-isomer is calculated to undergo very facile elimination of dihydrogen resulting from a dipolar H+...H- interaction between the ammonium groups. The trans-isomer is predicted to spontaneously dissociate to a complex of cyclopentene cation-radical and two ammonia molecules.