Can I read New Insights Into the Interconversion Mechanism Between Phenol and Its Isomers on EtoBox?

New Insights Into the Interconversion Mechanism Between Phenol and Its Isomers by Isabel Gómez; Elena Rodríguez; Mar Reguero is a Chemistry article available to read on EtoBox.

What is New Insights Into the Interconversion Mechanism Between Phenol and Its Isomers about?

We have studied the tautomerization reactions of 2,4-cyclohexadienone and 2,5-cyclohexadienone to phenol and the phenol dissociation to phenoxy radical using ab initio calculations. For the tautomerization mechanisms, the geometries were optimized at the CASSCF(8,8)/6-31G\* level and the energetics were recalculated at the CASPT2(8,8)/cc-pVDZ level. For the dissociation reaction, the computational requirements for achieving comparable accuracy were stricter. In this case, the geometry optimizations were carried out at the CASSCF(10,9)/6-31G\* level and the energetics were tuned with CASPT2(10,9)/aug-cc-pVTZ calculations. The tautomerization of 2,4-cyclohexadienone to phenol involved a onestep mechanism with a barrier of 53.3 kcal mol K1 , while the interconversion from 2,4-cyclohexadienone to 2,5-cyclohexadienone involved a twostep mechanism, which disagreed with previous theoretical results. This interconversion occurs through a diradical intermediate. The highest barrier, between the reactant and the intermediate, was of 42.7 kcal mol K1 . The best result for O-H bond dissociation enthalpy (BDE) of phenol to phenoxy was 86.2 kcal mol K1 , which is within the interval proposed for

Who reads New Insights Into the Interconversion Mechanism Between Phenol and Its Isomers?

Author

Isabel Gómez; Elena Rodríguez; Mar Reguero

Publisher

Elsevier Science; Elsevier ; Elsevier BV (ISSN 0166-1280)

Published

2006

Language

EN

Field

Chemistry (Physical Sciences)