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Remote Substituent Effects on Homolytic Bond Dissociation Energies.

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Title: Remote Substituent Effects on Homolytic Bond Dissociation Energies.
Authors: Yao Fu, Lei Liu, Bo-Lin Lin, Yi Mou, Yu-Hui Cheng, Qing-Xiang Guo
Source: Journal of Organic Chemistry. 6/13/2003, Vol. 68 Issue 12, p4657. 6p. 1 Diagram, 4 Charts, 6 Graphs.
Subjects: Dissociation (Chemistry), Hammett equation
Abstract: In the study we tried to answer two questions. First, does X-Z homolytic bond dissociation energy (BDE) of Y-C[sub 6]H[sub 4]-X-Z obey the Hammett relationship? Second, if it does what factors determine the magnitude and sign of the slope (ρ[sup +]) of Hammett regression against substituent σ[sub p, sup +] constants? We collected a large number of X-Z BDEs for over one-thousand Y-C[sub 6]H[sub 4]-X-Z systems using the RMP2/6-311++G[sup **]//UB3LYP/6-31G[sup *] method. We found that remote substituent effects on X-Z BDEs are determined by both the ground effect (i.e. stabilization/destabilization of X-Z by the substituents) and the radical effect (i.e. stabilization/destabilization of X[sup •] by the substituents). The ground or radical effect is determined by the electron demand of X-Z or X[sup •] in the same way as the deprotonation enthalpy of HOOC-C[sub 6]H[sub 4]-X-Z or HOOC-C[sub 6]H[sub 4]-X[sup •] is affected by X-Z or X[sup •]. As a result, ρ[sup +](BDE) for X-Z bond homolysis can be quantitatively predicted by using the change in deprotonation enthalpy from HOOC-C[sub 6]H[sub 4]-X-Z to HOOC-C[sub 6]H[sub 4]-X[sub •]. [ABSTRACT FROM AUTHOR]
Copyright of Journal of Organic Chemistry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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DbLabel: Engineering Source
An: 10077643
AccessLevel: 6
PubType: Academic Journal
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  Label: Title
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  Data: Remote Substituent Effects on Homolytic Bond Dissociation Energies.
– Name: Author
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  Data: <searchLink fieldCode="AR" term="%22Yao+Fu%22">Yao Fu</searchLink><br /><searchLink fieldCode="AR" term="%22Lei+Liu%22">Lei Liu</searchLink><br /><searchLink fieldCode="AR" term="%22Bo-Lin+Lin%22">Bo-Lin Lin</searchLink><br /><searchLink fieldCode="AR" term="%22Yi+Mou%22">Yi Mou</searchLink><br /><searchLink fieldCode="AR" term="%22Yu-Hui+Cheng%22">Yu-Hui Cheng</searchLink><br /><searchLink fieldCode="AR" term="%22Qing-Xiang+Guo%22">Qing-Xiang Guo</searchLink>
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+Organic+Chemistry%22">Journal of Organic Chemistry</searchLink>. 6/13/2003, Vol. 68 Issue 12, p4657. 6p. 1 Diagram, 4 Charts, 6 Graphs.
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  Data: <searchLink fieldCode="DE" term="%22Dissociation+%28Chemistry%29%22">Dissociation (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Hammett+equation%22">Hammett equation</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: In the study we tried to answer two questions. First, does X-Z homolytic bond dissociation energy (BDE) of Y-C[sub 6]H[sub 4]-X-Z obey the Hammett relationship? Second, if it does what factors determine the magnitude and sign of the slope (ρ[sup +]) of Hammett regression against substituent σ[sub p, sup +] constants? We collected a large number of X-Z BDEs for over one-thousand Y-C[sub 6]H[sub 4]-X-Z systems using the RMP2/6-311++G[sup **]//UB3LYP/6-31G[sup *] method. We found that remote substituent effects on X-Z BDEs are determined by both the ground effect (i.e. stabilization/destabilization of X-Z by the substituents) and the radical effect (i.e. stabilization/destabilization of X[sup •] by the substituents). The ground or radical effect is determined by the electron demand of X-Z or X[sup •] in the same way as the deprotonation enthalpy of HOOC-C[sub 6]H[sub 4]-X-Z or HOOC-C[sub 6]H[sub 4]-X[sup •] is affected by X-Z or X[sup •]. As a result, ρ[sup +](BDE) for X-Z bond homolysis can be quantitatively predicted by using the change in deprotonation enthalpy from HOOC-C[sub 6]H[sub 4]-X-Z to HOOC-C[sub 6]H[sub 4]-X[sub •]. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Journal of Organic Chemistry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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RecordInfo BibRecord:
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    Identifiers:
      – Type: doi
        Value: 10.1021/jo034094h
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      – Code: eng
        Text: English
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        PageCount: 6
        StartPage: 4657
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      – SubjectFull: Dissociation (Chemistry)
        Type: general
      – SubjectFull: Hammett equation
        Type: general
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      – TitleFull: Remote Substituent Effects on Homolytic Bond Dissociation Energies.
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            NameFull: Yao Fu
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            NameFull: Lei Liu
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            NameFull: Bo-Lin Lin
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            NameFull: Yi Mou
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            NameFull: Yu-Hui Cheng
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            NameFull: Qing-Xiang Guo
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            – D: 13
              M: 06
              Text: 6/13/2003
              Type: published
              Y: 2003
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              Value: 68
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              Value: 12
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            – TitleFull: Journal of Organic Chemistry
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