Abstract
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.
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Literature cited
R. C. Fort, Adamantane: The Chemistry of Molecules, Marcel Dekker, New York (1976).
J. J. Ritter and P. Minieri, “A new reaction of nitriles. 1. Amides from alkenes and mononitriles,” J. Am. Soc.,70, No. 5, 4045–4048 (1948).
G. A. Olah and J. Lukas, “Stable carbonium ions. Protonation of and hydride ion abstraction from cycloalkanes and polycycloalkanes in fluorosulfonic acid-antimony pentafluoride,” ibid.,90, No. 4, 933–938 (1968).
J. Tabushi, Y. Aoyama, and S. Kojo, “Free-radical halogenation of adamantane. Selectivity and relative lifetime of 1- and 2-adamantyl radicals,” ibid.,94, NO. 4, 1177–1183 (1972).
J. S. Lomas and J. E. Dubois, “Formation of alkyl carbanions by alkoxide fragmentation in HMPT,” J. Org. Chem.,49, No. 11, 2067–2069 (1984).
R. A. Rossi, S. M. Palacios, and A. N. Santiago, “Reaction of 1-bromoadamantane with diphenylphosphide and diphenylarsenide ions by the SRN1 mechanism,” ibid.,47, No. 24, 4654–4657 (1982).
T. Holm, “Electron transfer from alkylmagnesium compounds to organic substrates,” Acta Chem. Scand., B,37, No. 4, 567–584 (1983).
G. Molle, S. Briand, P. Bauer, and J. E. Dubois, “Synthèse de molecules encombrées. Recherche des conditions optimales de condensation des composes organolithiens cagè sur diffèrents substrats organiques,” Tetrahedron,40, No. 24, 5113–5119 (1984).
R. C. Bingham, M. J. S/ Dewar, and D. H. Jo, “Ground states of molecules. MINDO/3, An improved version of the MINDO semiempirical SCF-MO method,” J. Am. Chem. Soc.,97, No. 6, 1285–1293 (1975).
V. V. Lobanov, “Program for calculating macroscopic properties of substances on the basis of data from calculations in the semiempirical MINDO/3 approximation,” Zh. Strukt. Khim.,26, No. 6, 126–127 (1985).
P. V. R. Schleyer, “Conformational analysis of bridgehead carbonium ions,” J. Am. Chem. Soc.,89, No. 3, 582–593 (1967).
D. E. Sunko, S. Hirse, S. K. Pollack, and W. J. Hehre, “Hyperconjugation and homohyperconjugation in the 1-adamantyl cation,” ibid.,101, No. 21, 6163–6170 (1970).
R. J. Gillespie, Molecular Geometry, Van Nostrand Reinhold, New York (1972).
G. H. Kruppa and J. L. Beauchamp, “Energetic and structure of the 1- and 2-adamantyl radicals and their corresponding carbonium ions by photoelectron spectroscopy,” J. Am. Chem. Soc.,108, No. 9, 2162–2169 (1986).
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Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 3, pp. 357–360, May–June, 1989.
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Yurchenko, A.G., Lobanov, V.V., Fedorenko, T.V. et al. Quantum-chemical study of the electronic structure of adamantane and the 1-adamantyl cation, anion, and radical. Theor Exp Chem 25, 331–334 (1989). https://doi.org/10.1007/BF01299015
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DOI: https://doi.org/10.1007/BF01299015