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; Büsra Dereli; Larry Que; Chris Cramer

doi:10.1039/c6cc05395e

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, Büsra Dereli, Larry Que, Chris Cramer

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

22 Scopus citations

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.

Original language	English (US)
Pages (from-to)	10509-10512
Number of pages	4
Journal	Chemical Communications
Volume	52
Issue number	69
DOIs	https://doi.org/10.1039/c6cc05395e
State	Published - 2016

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© The Royal Society of Chemistry 2016.

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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.",

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AU - Klein, Johannes E.M.N.

AU - Dereli, Büsra

AU - Que, Larry

AU - Cramer, Chris

N1 - Publisher Copyright: © The Royal Society of Chemistry 2016.

PY - 2016

Y1 - 2016

N2 - 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.

AB - 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.

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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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