Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 2009-06-11

Energetics of tert-butoxyl addition reaction to norbornadiene: a method for estimating the pi-bond strength of a carbon-carbon double bond.

Paulo M Nunes, Sílvia G Estácio, Gustavo T Lopes, Filipe Agapito, Rui C Santos, Benedito J Costa Cabral, Rui M Borges dos Santos, José A Martinho Simões

Index: J. Phys. Chem. A 113(23) , 6524-30, (2009)

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Abstract

The energetics of tert-butoxyl radical addition reaction to norbornadiene was investigated by time-resolved photoacoustic calorimetry (TR-PAC). The result, together with the C-O bond dissociation enthalpy (BDE) in the addition product, allowed us to calculate the pi-bond dissociation enthalpy in norbornadiene. Quantum chemistry (QC) methods were also used to obtain several enthalpies of reaction of the addition of oxygen-centered radicals to alkenes. The pi-bond dissociation enthalpies in these molecules were calculated by a procedure similar to that used in the case of norbornadiene and were compared with the pi-BDE values obtained by the method proposed by Benson. These two different approaches yield similar values for the pi-BDEs in alkenes, indicating that the addition method proposed in the present study is a valid way to derive that quantity. The influence of strain in the pi-BDEs of cyclic alkenes was investigated and allowed us to justify the difference between the pi-BDE in norbornene and norbornadiene. Finally, the thermochemistry of the addition and abstraction reactions involving these two molecules and tert-butoxyl radical was analyzed.