Demonstration of tunable reactivity for meta-benzynes

John J. Nash; Katrina E. Nizzi; Anthony Adeuya; Michael J. Yurkovich; Christopher J. Cramer; Hilkka I. Kenttämaa

doi:10.1021/ja0449473

Demonstration of tunable reactivity for meta-benzynes

John J. Nash, Katrina E. Nizzi, Anthony Adeuya, Michael J. Yurkovich, Christopher J. Cramer, Hilkka I. Kenttämaa

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

27 Scopus citations

Abstract

A combined computational and experimental study on the gas-phase structures and reactivities of charged 1,3-didehydroarenes (meta-benzynes) demonstrates that the reactivity of such biradicals can be "tuned" by using appropriate substituents. Substituents that destabilize a specific zwitterionic resonance structure can change the reactivity of the biradical from mildly carbocationic to radical-like. These substituent effects are not the result of changes in the singlet-triplet gaps of the biradicals, but rather reflect changes in the potential energy surfaces for the dehydrocarbon separation.

Original language	English (US)
Pages (from-to)	5760-5761
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	127
Issue number	16
DOIs	https://doi.org/10.1021/ja0449473
State	Published - Apr 27 2005
Externally published	Yes

Access

10.1021/ja0449473

OpenUrl availability

Full text

Cite this

@article{ea1104e9c6af4e879b2c60d70d0e1c6a,

title = "Demonstration of tunable reactivity for meta-benzynes",

abstract = "A combined computational and experimental study on the gas-phase structures and reactivities of charged 1,3-didehydroarenes (meta-benzynes) demonstrates that the reactivity of such biradicals can be {"}tuned{"} by using appropriate substituents. Substituents that destabilize a specific zwitterionic resonance structure can change the reactivity of the biradical from mildly carbocationic to radical-like. These substituent effects are not the result of changes in the singlet-triplet gaps of the biradicals, but rather reflect changes in the potential energy surfaces for the dehydrocarbon separation.",

author = "Nash, {John J.} and Nizzi, {Katrina E.} and Anthony Adeuya and Yurkovich, {Michael J.} and Cramer, {Christopher J.} and Kentt{\"a}maa, {Hilkka I.}",

year = "2005",

month = apr,

day = "27",

doi = "10.1021/ja0449473",

language = "English (US)",

volume = "127",

pages = "5760--5761",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "16",

}

TY - JOUR

T1 - Demonstration of tunable reactivity for meta-benzynes

AU - Nash, John J.

AU - Nizzi, Katrina E.

AU - Adeuya, Anthony

AU - Yurkovich, Michael J.

AU - Cramer, Christopher J.

AU - Kenttämaa, Hilkka I.

PY - 2005/4/27

Y1 - 2005/4/27

N2 - A combined computational and experimental study on the gas-phase structures and reactivities of charged 1,3-didehydroarenes (meta-benzynes) demonstrates that the reactivity of such biradicals can be "tuned" by using appropriate substituents. Substituents that destabilize a specific zwitterionic resonance structure can change the reactivity of the biradical from mildly carbocationic to radical-like. These substituent effects are not the result of changes in the singlet-triplet gaps of the biradicals, but rather reflect changes in the potential energy surfaces for the dehydrocarbon separation.

AB - A combined computational and experimental study on the gas-phase structures and reactivities of charged 1,3-didehydroarenes (meta-benzynes) demonstrates that the reactivity of such biradicals can be "tuned" by using appropriate substituents. Substituents that destabilize a specific zwitterionic resonance structure can change the reactivity of the biradical from mildly carbocationic to radical-like. These substituent effects are not the result of changes in the singlet-triplet gaps of the biradicals, but rather reflect changes in the potential energy surfaces for the dehydrocarbon separation.

UR - http://www.scopus.com/inward/record.url?scp=17744367443&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=17744367443&partnerID=8YFLogxK

U2 - 10.1021/ja0449473

DO - 10.1021/ja0449473

M3 - Article

C2 - 15839653

AN - SCOPUS:17744367443

SN - 0002-7863

VL - 127

SP - 5760

EP - 5761

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 16

ER -

Demonstration of tunable reactivity for meta-benzynes

Abstract

Access

OpenUrl availability

Other files and links

Fingerprint

Cite this