| Publication Type |
Journal Article |
| Title |
Energetics of tert-Butoxyl Addition Reaction to Norbornadiene: A Method for Estimating the pi-Bond Strength of a Carbon-Carbon Double Bond |
| Authors |
Paulo M. Nunes Silvia G. Estacio Gustavo T. Lopes Filipe Agapito R.M. Borges dos Santos Benedito J. Costa Cabral Jose A. Martinho Simoes |
| Groups |
|
| Journal |
JOURNAL OF PHYSICAL CHEMISTRY A |
| Year |
2009 |
| Month |
June |
| Volume |
113 |
| Number |
23 |
| Pages |
6524-6530 |
| 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. |
| DOI |
http://dx.doi.org/10.1021/jp900089t |
| ISBN |
|
| Publisher |
AMER CHEMICAL SOC |
| Book Title |
|
| ISSN |
1089-5639 |
| EISSN |
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| Conference Name |
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| Bibtex ID |
ISI:000266679100018 |
| Observations |
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