Why metal-oxos react with dihydroanthracene and cyclohexadiene at comparable rates, despite having different C-H bond strengths. A computational study

Johannes E. M. N. Klein; Busra Dereli; Lawrence Que; Christopher J. Cramer

doi:10.1039/c6cc05395e

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Why metal-oxos react with dihydroanthracene and cyclohexadiene at comparable rates, despite having different C-H bond strengths. A computational study

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Why metal-oxos react with dihydroanthracene and cyclohexadiene at comparable rates, despite having different C-H bond strengths. A computational study

Johannes E. M. N. Klein, Busra Dereli, Lawrence Que and Christopher J. Cramer

Chemical communications (Cambridge, England), Vol.52(69), pp.10509-10512

01/01/2016

DOI: https://doi.org/10.1039/c6cc05395e

PMID: 27489080

Abstract

Chemistry

Chemistry, Multidisciplinary

Physical Sciences

Science & Technology

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 similar to 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.

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Title: Why metal-oxos react with dihydroanthracene and cyclohexadiene at comparable rates, despite having different C-H bond strengths. A computational study
Creators - without role: Johannes E. M. N. Klein - University of Minnesota
Busra Dereli - University of Minnesota
Lawrence Que - University of Minnesota
Christopher J. Cramer - University of Minnesota
Publication Details: Chemical communications (Cambridge, England), Vol.52(69), pp.10509-10512
Publisher: Royal Soc Chemistry
Number of pages: 4
Grant note: R01GM038767 / NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES; United States Department of Health & Human Services; National Institutes of Health (NIH) - USA; NIH National Institute of General Medical Sciences (NIGMS) 1361595 / Direct For Mathematical & Physical Scien; National Science Foundation (NSF); NSF - Directorate for Mathematical & Physical Sciences (MPS) Alexander von Humboldt Foundation 1361773 / Division Of Chemistry; National Science Foundation (NSF); NSF - Directorate for Mathematical & Physical Sciences (MPS) CHE-1361595; CHE-1361773 / National Science Foundation; National Science Foundation (NSF)
Identifiers: 9944685508331
Academic Unit: King Abdullah University of Science & Technology
Language: English
Resource Type: Journal article