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Effect of medium on the rate constant of decarbonylation of phenylacetyl radical |
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| Authors: | Tsentalovich Yu P Kurnysheva O A Gritsan N P |
| Institution: | (1) International Tomography Center, Siberian Branch of the Russian Academy of Sciences, 3a ul. Institutskaya, 630090 Novosibirsk, Russian Federation;(2) Novosibirsk State University, 2 ul. Pirogova, 630090 Novosibirsk, Russian Federation;(3) Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, 3 ul. Institutskaya, 630090 Novosibirsk, Russian Federation |
| Abstract: | The rate constant k
CO of decarbonylation of phenylacetyl radicals generated by photolysis of dibenzyl ketone was measured by laser flash photolysis technique in six solvents in a wide temperature range. The pre-exponential factors A and activation energies E
a of decarbonylation were found for all solvents. The k
CO value decreases with an increase in the dielectric constant  of the solvent, whereas an increase in the ability of the solvent for hydrogen bonding increases k
CO. The results of quantum-chemical calculations confirm the mutual compensation of the contributions of specific and nonspecific solvations to the activation energy of decarbonylation in alcohols. |
| Keywords: | laser flash photolysis radical fragmentation decarbonylation phenylacetyl radical quantum-chemical calculations |
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