Thermal Decomposition of the Benzyl Radical to Fulvenallene (C7H6) H
Gabriel da Silva, John A Cole, Joseph W Bozzelli
JOURNAL OF PHYSICAL CHEMISTRY A | AMER CHEMICAL SOC | Published : 2009
We show that the benzyl radical decomposes to the C7H6 fragment fulvenallene (+H), by first principles/RRKM study. Calculations using G3X heats of formation and B3LYP/6-31G(2df,p) structural and vibrational parameters reveal that the reaction proceeds predominantly via a cyclopentenyl-allene radical intermediate, with an overall activation enthalpy of ca. 85 kcal mol(-1). Elementary rate constants are evaluated using Eckart tunneling corrections, with variational transition state theory for barrierless C-H bond dissociation in the cyclopentenyl-allene radical. Apparent rate constants are obtained as a function of temperature and pressure from a time-dependent RRKM study of the multichannel m..View full abstract
Awarded by U.S. Air Force Phase II STTR
This research was partially Supported by the U.S. Air Force Phase II STTR (contract number FA865006-C-2658).