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

29 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.",

author = "Klein, \{Johannes E.M.N.\} and B{\"u}sra Dereli and Larry Que and Chris Cramer",

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year = "2016",

doi = "10.1039/c6cc05395e",

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T1 - Why metal-oxos react with dihydroanthracene and cyclohexadiene at comparable rates, despite having different C-H bond strengths. A computational study

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.

UR - https://www.scopus.com/pages/publications/84983661452

UR - https://www.scopus.com/pages/publications/84983661452#tab=citedBy

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DO - 10.1039/c6cc05395e

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AN - SCOPUS:84983661452

SN - 1359-7345

VL - 52

SP - 10509

EP - 10512

JO - Chemical Communications

JF - Chemical Communications

IS - 69

ER -

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

Abstract

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