Abstract
Very low-pressure pyrolysis (VLPP) of the title compounds indicates both C-C and C-H bond rupture. Rate constants for all six processes are compatible with A factors of 10/sup 15.3/ s/sup -1/ and activation energies of 81.4 kcal mol/sup -1/ for C-H rupture in diphenylmethane and 82.3 kcal mol/sup -1/ for all the other C-H and C-C bond-breaking processes. The derived heat of formation of diphenylmethyl radical is 69.0 kcal mol/sup -1/. This is in excellent agreement with other studies and indicates that C-H bond rupture in phenylmethanes behaves analogously to C-C rupture. The extra stabilization in diphenylmethyl radical when compared with ..cap alpha..-phenylethyl radical is approx. 4 kcal mol/sup -1/.
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