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The a p p r o a c h of triplet carbene to m e t h a n e ; a) direct insertion; b) abstraction. Reaction coordinate for abstraction r = bl - - b~ + 2 Experimental results are in greement with these findings. Calculations were also performed for the reaction of singlet methylene, with both ethylene and methane: paths in which no activation energy is involved can be found in both cases. ,-~. 0 kcal/mole, respectively 185). Other applications are studies of: rotation about double bonds 186), ring inversion in cyclooctatetraene 187), the insertion of carbon into ethylene and trans-2-butene to give allenes 138), the barrier height to inversion of nitrogen in hydrazine and alkylamines 139), the Cope 33 M.

Abrahamson, E. : J. Am. Chem. Soc. 87, 2045 (1965). , Woodward, R. : J. Am. Chem. Soc. 87, 2046 (1965). 5) Ref. 1, page 65. , Woodward, R. : J. Am. Chem. Soc. 87, 4388 (1965). 7) Woodward, R. : J. Am. Chem. Soc. 87, 2511 (1965). 8) Holder, R. W. : quoted in Ref. 9). 9) Berson, J. A. : Accounts Chem. Res. 5, 406 (1972). 10) Berson, J. : J. Am. Chem. Soc. g4, 8917 (1972). : Angew. Chem. Intern. Ed. Engl. 17, 92 (1972). 12) Baldwin, J. , Andrist, A. , Pinschmidt, R. , Jr. : A c c . Chem. Res. 5, 402 (1972).

Menton, July 1970. 44) Simonetta, M. : in the press. 45) Dewar, M. J. S. : In: Advances in Chemical Physics VIII, p. 65 (ed. R. Daudel). New York: Interscience Publ. 1965. 46) Hudson, R. : Angew. Chem. Intern. Ed. EngL 12, 36 (1973). 47) Herndon, W. : Chem. Rev. 72, 157 (1972). : J. Am. Chem. Soc. 86, 4550 (1964). : J. Am. Chem. Soc. 87, 3300 (1965). , Hudson, R. : Theoret. Chim. Acta 8, 165 (1967). 51) Dougherty, R. : J. Am. Chem. Soc. 93, 7187 (1971). , Pozzoli, A. , Del Re, G. : Perkin Trans II 1972, 1572.

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