With reference to J. Am. Chem. Soc. 1968, 90 (19), 5266–5267, they state:

The most favorable geometry of aliphatic free radicals remains an unsolved problem, since existing data are consistent with a geometry which is either pyramidal and rapidly inverting, or planar but easily deformed.2-4 One approach to the problem is generation of the radical at a bridgehead of a bridged bicyclic system. [...] From their aldehyde decarbonylation study, however, Applequist and Kaplan concluded that 1 -adamantyl and 1 -bicyclo[2.2.2]octyl were appreciably more stable than t-butyl. 3
3. J. Am. Chem. Soc. 1965, 87 (10), 2194–2200

which is later concluded as:

[...] The extent of geometrical destabilization is considerable, and we conclude that alkyl radicals tend toward planar geometry. The lesser extent of destabilization, relative to that for the carbonium ions, might mean that radicals seek a flattened pyramidal state. [...] This issue can evidently not be settled without spectroscopic information about alkyl radicals.

Has there been any further studies on the geometry of free radicals at the bridgehead carbon?

  • $\begingroup$ If you have access to Science Citation Index, you may locate more recent work. $\endgroup$
    – user55119
    Sep 13, 2020 at 15:21
  • $\begingroup$ @user55119 unfortunately I do not.. Could you share a reference if possible? $\endgroup$ Sep 13, 2020 at 16:06
  • $\begingroup$ I found 115. I'll see what I can do. $\endgroup$
    – user55119
    Sep 13, 2020 at 20:06
  • 2
    $\begingroup$ These 2 are dated but perhaps of interest. STABILITY OF ADAMANT-1-YL RADICAL JOURNAL OF THE CHEMICAL SOCIETY D-CHEMICAL COMMUNICATIONS Issue: ‏ 5 Pages: ‏ 216-& Published: ‏ 1969 . BRIDGEHEAD FREE RADICAL STABILITY . DECOMPOSITION OF T-BUTYLPEROXYESTERS OF 1-ADAMANTYL 1-BICYCLO[2.2.]OCTYL AND 1-NORBORNYL SYSTEMS CANADIAN JOURNAL OF CHEMISTRY Volume: ‏ 46 Issue: ‏ 19 Pages: ‏ 3099-& Published: ‏ ‏ 1968 $\endgroup$
    – user55119
    Sep 13, 2020 at 20:54
  • $\begingroup$ @user55119 Thanks.. I was also able to find a comprehensive paper regarding bridgehead radicals Chem. Soc. Rev. 1992, 21 (2), 105 by John C. Walton $\endgroup$ Sep 19, 2020 at 17:24


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