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Ionization potentials, electron affinities, and molecular orbitals of 2-substituted norbornadienes. Theory of 1,2 and homo-1,4 carbene cycloaddition selectivities

Published inJournal of the American Chemical Society, vol. 105, no. 17, p. 5563-5569
Publication date1983
First online date2002-05-01
Abstract

The ionization potentials, electron affinities, and π orbital shapes of 2-substituted norbornadienes have been determined by photoelectron spectroscopy, electron-transmission spectroscopy, and ab initio molecular orbital calculations, respectively. The deductions made about the electronic structures of 2-methoxy-, (trimethylsiloxy)-, chloro-, cyano-, (methoxycarbonyl)-, and phenylnorbornadienes permit a detailed interpretation of the reactivities and selectivities observed experimentally in carbene cycloadditions to these molecules. A substituent at C-2 of norbornadiene not only affects the 2-3 π bond but also influences the 5-6 π bond due to through-space interactions between π orbitals. The orbital energy changes and polarization induced by 2-substituents provide a compelling rationale of the variations in 1,2 and homo-1,4 cycloadditions of carbenes to these species, and confirm the electrophilic nature of both of these cycloadditions.

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Citation (ISO format)
HOUK, K.N. et al. Ionization potentials, electron affinities, and molecular orbitals of 2-substituted norbornadienes. Theory of 1,2 and homo-1,4 carbene cycloaddition selectivities. In: Journal of the American Chemical Society, 1983, vol. 105, n° 17, p. 5563–5569. doi: 10.1021/ja00355a006
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ISSN of the journal0002-7863
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