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| - Role of Charge-Transfer Configurations on the AdditionReaction of Aminoalkyl Radicals onto Acrylate Double Bonds
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| Abstract
| - The major factors affecting the reactivity of the important class of aminoalkyl radicals toward theaddition reaction onto acrylate double bonds were studied. The rate constants of interaction, directlymeasured by using laser-induced photoacoustic calorimetry, range from 2.5 × 107 to 4.5 × 107 M-1 s-1.The reactivity of these radicals was compared to that of alkyl radicals. Calculations show that the reactionenthalpy is not the driving factor. Molecular orbital calculations of the transition states clearly demonstratedthe large participation of charge-transfer configurations relative to nonpolar configurations, leading to adecrease of the barrier height. Moreover a quite good correlation is found when plotting the charge-transfercharacter in the transition state against the ionization potential. The roles of the different factors governingthe reactivity of these species were elucidated.
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