Journal of the Chemical Society. Perkin transactions II p. 2169 - 2176 (1989)
Update date:2022-07-29
Topics:
Walton, John C.
E.s.r observation of radicals derived from 9-bromtricyclo<3.3.1.02,8>nona-3,6-diene, and related compounds, showed that they rearrange by β-scission to bicyclo<3.2.2>nona-2,6,8-trienyl radicals extremly rapidly; the latter radicals have hyperfine splittings similar to those of allyl radicals. 9-Deuterio- and 2-deuterio-9-bromotricyclo<3.3.1.02,8>nona-3,6-diene were reduced with tributyltin hydride.The pattern of deuterium scrambling in the bicyclo<3.2.2>nona-2,6,8-triene and tricyclo<3.3.1.02,8>nona-3,6-diene products showed that the intermediate radicals take part in a degenerate rearrangement sequence which makes them fully fluxional in three dimensions.The two radicals are in equilibrium at ca. 375 K, but the bicyclotrienyl species is more important by a factor of ca. 102.Neither the experimental results nor MNDO semiempirical calculations provided any evidence of additional thermodynamic stabilisation in the radical pair beyond that expected for allyl delocalisation.
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