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

26 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

Bibliographical note

Publisher Copyright:
© The Royal Society of Chemistry 2016.

Publisher link

10.1039/c6cc05395e

Find It

Find It at U of M Libraries

Cite this

@article{eeed25d9ffc040c2a049b43df85aa430,

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.",

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

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2016.",

year = "2016",

doi = "10.1039/c6cc05395e",

language = "English (US)",

volume = "52",

pages = "10509--10512",

journal = "Chemical Communications",

issn = "1359-7345",

publisher = "Royal Society of Chemistry",

number = "69",

}

TY - JOUR

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 - http://www.scopus.com/inward/record.url?scp=84983661452&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84983661452&partnerID=8YFLogxK

U2 - 10.1039/c6cc05395e

DO - 10.1039/c6cc05395e

M3 - Article

C2 - 27489080

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

Bibliographical note

Publisher link

Find It

Other files and links

Fingerprint

Cite this