Trisubstituted methyl radicals

Trisubstituted carbon-centred radicals chemically appear planar as depicted in the TT-type structure 1. However, spectroscopic studies have shown that planarity holds only for methyl, which has a very shallow well for inversion with a planar energy minimum, and for delocalized radical centres like allyl or benzyl. Ethyl, isopropyl, tert-butyl and all the like have double minima for inversion but the barrier is only about 300-500 cal, so that inversion is very fast even at low temperatures. Moreover, carbon-centred radicals with electronegative substituents like alkoxyl or fluorine reinforce the non-planarity, the effect being accumulative for multi-substitutions. This is ascribed to no bonds between n electrons on the heteroatom and the bond to another substituent. The degree of bending is also increased by ring strain like in cyclopropyl and oxiranyl radicals, whereas the disubstituted carbon-centred species like vinyl or acyl are bent a radicals [21]. 

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