APPLICATION OF THE THEORY OF ATOMS IN MOLECULES TO THE BORANES AND CARBORANES

Abstract

The theory of Atoms in Molecules is applied to a series of borane molecules. A study of the topological features of the charge density, p(r), yields a quantum mechanical definition of atoms, bonds, and the average properties of atoms within a molecule. Other topological features of the boranes studied include rings and cages, formed by bond paths in p which link the atoms. These bond paths which form rings are bent inward in order to maximize the binding in these electron-deficient molecules. An important result of this analysis is the unambiguous assignment of the connectivity of the boranes. The theory of atoms and molecules allows one to quantum mechanically partition molecules into atomic basins, and calculations of average values for electron count and energies of individual atoms are performed by integration over these basins. Comparisons of atomic properties are performed to determine the transferability of atomic properties across the series. The Laplacian of p, V2p, yields information about sites of electrophilic and nucleophilic attack in molecules. These sites are found to correspond to the positions of critical points in V2p, which are localized to specific atoms in the molecule. The boranes and carboranes are ranked according to their susceptibility to electrophilic and nucleophilic attack, and such reactions with boranes are predicted to be regiospecific.