Quantum-chemical study of the electronic structure of adamantane and the 1-adamantyl cation,anion, and radical

The spatial and electronic structures of the adamantane molecule (AdH), the 1-adamantyl radical (1-Ad^.), the 1-adamantyl cation (1-AD⁺), and the 1-adamantyl anion (1-Ad^–) have been calculated by the SCF-MO-LCAO method in the all-valence-electron MINDO approximation. The calculated heats of formation attest to the fact that the homolytic cleavage of the C-H bond is energetically most advantageous in the gaseous phase or in nonpolar inert solvents. The formation of a 1-Ad^–, H⁺ pair is associated with the largest expenditure of energy due to the large ionization potential of the hydrogen atom.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 3, pp. 357–360, May–June, 1989.