Electronic aspects of the hydride transfer mechanism. III. Ab-initio analytical gradient studies of the cyclopropenyl-cation/LiH with 4-31G and 3-21+G basis sets.

Abstract Hydride transfer reaction have been studied in sections of the energy hypersurface of cyclopropenyl cation and lithium hydride at 4-31G and 3-21+G basis set levels. The diffuse component has enforced the idea of an hydride-ion as being the particle transferred in the ground electronic state. Calculations on the first triplet state suggest a transfer mechanism mediated by one-electron followed by an hydrogen atom transfer. The change of basis set does not affect structural and energetics aspects of the reacting system except for the transferred particle, where, for some molecular complexes, the electronic distribution can be described as a hydride ion cementing two electron defficie…