title: Why metal-oxos react with dihydroanthracene and cyclohexadiene at comparable rates, despite having different C-H bond strengths. A computational study.
abstract: 1,4-Cyclohexadiene (CHD) and 9,10-dihydroanthracene (DHA) are two substrates used to probe the steric requirements of metal-oxo oxidants in H-atom-transfer (HAT) reactions, based on the assumption that they have comparable C-H bond dissociation enthalpies (BDEs). We use computations to demonstrate that the BDE of DHA is ∼3.5 kcal mol(-1) larger than that of CHD and that their often comparable reactivity is based on a competing interplay of bond strengths and favorable van der Waals interactions.
authors.affiliation: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. S.E., Minneapolis, Minnesota 55455, USA. kleinj@umn.edu.
authors.forename: Johannes E M N
authors.initials: JE
authors.lastname: Klein
authors.affiliation: Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota, 207 Pleasant Street S.E., Minneapolis, Minnesota 55455, USA.
authors.forename: Büsra
authors.initials: B
authors.lastname: Dereli
authors.affiliation: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. S.E., Minneapolis, Minnesota 55455, USA. kleinj@umn.edu.
authors.forename: Lawrence
authors.initials: L
authors.lastname: Que
authors.affiliation: Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota, 207 Pleasant Street S.E., Minneapolis, Minnesota 55455, USA.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Cramer