The BDE of 3,5-di-tert-butylcatechol (78.2 kcal mol(-1)) was determined to be identical to that of a-tocopherol. Through use of the group additivity rule, this piece of data was also used to calculate the strength of the intramolecular hydrogen bond between the hydroxyl proton and the oxygen radical centre in the corresponding semiquinone radical (5.6 kcal mol(-1)), which is responsible both for the excellent antioxidant properties of catechols and for the BIDE of catechol (81.8 kcal mol(-1)). These values are in poor agreement with those predicted by DFT calculations reported in the literature (9.5 kcal mol(-1) and 77.6 kcal mol(-1), respectively). Extensive theoretical calculations indicate that the BIDE of catechol is reproduced well (81.6 kcal mol(-1)) by use of diffuse functions on oxygen and the CCSD method.
A critical evaluation of the factors determining the effect of intramolecular hydrogen bonding on the O-H bond dissociation einithalpy of catechol and of flavonoid antioxidants
Guerra M
2004
Abstract
The BDE of 3,5-di-tert-butylcatechol (78.2 kcal mol(-1)) was determined to be identical to that of a-tocopherol. Through use of the group additivity rule, this piece of data was also used to calculate the strength of the intramolecular hydrogen bond between the hydroxyl proton and the oxygen radical centre in the corresponding semiquinone radical (5.6 kcal mol(-1)), which is responsible both for the excellent antioxidant properties of catechols and for the BIDE of catechol (81.8 kcal mol(-1)). These values are in poor agreement with those predicted by DFT calculations reported in the literature (9.5 kcal mol(-1) and 77.6 kcal mol(-1), respectively). Extensive theoretical calculations indicate that the BIDE of catechol is reproduced well (81.6 kcal mol(-1)) by use of diffuse functions on oxygen and the CCSD method.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
