Effect of substituents on the preferred modes of one-electron reductive cleavage of N-Cl and N-Br bonds

Robert J. O'Reilly, Amir Karton, Leo Radom

Research output: Contribution to journalArticle

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Abstract

In this study, we investigate the effect of substituents in determining the modes of one-electron reductive cleavage of X-NRR′ (X = Cl and Br) molecules. We achieve this through comparison of the calculated gas-phase electron affinities (EAs) and aqueous-phase one-electron reduction potentials (E 's) for a range of nitrogen-centered radicals (NRR′) with the corresponding EA and E values for Cl and Br. The gas-phase EAs have been obtained using the benchmark-quality W1w thermochemical protocol, whereas E values have been obtained by additionally applying free energy of solvation corrections, obtained using the conductor-like polarizable continuum (CPCM) model. We find that the N-halogenated derivatives of amines and amides should generally cleave in such a way as to afford NRR′ and X-. For the N-halogenated imides, on the other hand, the N-brominated derivatives are predicted to produce Br in solution, whereas the N-chlorinated derivatives again would give Cl-. Importantly, we predict that N-bromouracil is likely to afford Br. This may have important implications in terms of inflammatory-related diseases, because Br may damage biomolecules such as proteins and DNA. To assist in the determination of the gas-phase EAs of larger NRR′ radicals, not amenable to investigation using W1w, we have evaluated the performance of a wide range of lower-cost theoretical methods. Of the standard density functional theory (DFT) procedures, M06-2X, τ-HCTHh, and B3-LYP show good performance, with mean absolute deviations (MADs) from W1w of 4.8-6.8 kJ mol-1, whereas ROB2-PLYP and B2-PLYP emerge as the best of the double-hybrid DFTs (DHDFTs), with MADs of 2.5 and 3.0 kJ mol-1, respectively. Of the Gn-type procedures, G3X and G4 show very good performance (MADs = 2.4 and 2.6 kJ mol-1, respectively). The G4(MP2)-6X+ procedure performs comparably, with an MAD of 2.7 kJ mol-1, with the added advantage of significantly reduced computational expense.

Original languageEnglish
Pages (from-to)460-472
Number of pages13
JournalJournal of Physical Chemistry A
Volume117
Issue number2
DOIs
Publication statusPublished - Jan 17 2013
Externally publishedYes

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Electron affinity
cleavage
electron affinity
Nitrogen
Electrons
Gases
deviation
nitrogen
Derivatives
vapor phases
electrons
Bromouracil
Imides
Solvation
Biomolecules
Discrete Fourier transforms
Amides
Free energy
Amines
imides

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Effect of substituents on the preferred modes of one-electron reductive cleavage of N-Cl and N-Br bonds. / O'Reilly, Robert J.; Karton, Amir; Radom, Leo.

In: Journal of Physical Chemistry A, Vol. 117, No. 2, 17.01.2013, p. 460-472.

Research output: Contribution to journalArticle

O'Reilly, Robert J. ; Karton, Amir ; Radom, Leo. / Effect of substituents on the preferred modes of one-electron reductive cleavage of N-Cl and N-Br bonds. In: Journal of Physical Chemistry A. 2013 ; Vol. 117, No. 2. pp. 460-472.
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N2 - In this study, we investigate the effect of substituents in determining the modes of one-electron reductive cleavage of X-NRR′ (X = Cl and Br) molecules. We achieve this through comparison of the calculated gas-phase electron affinities (EAs) and aqueous-phase one-electron reduction potentials (E 's) for a range of nitrogen-centered radicals (•NRR′) with the corresponding EA and E values for •Cl and •Br. The gas-phase EAs have been obtained using the benchmark-quality W1w thermochemical protocol, whereas E values have been obtained by additionally applying free energy of solvation corrections, obtained using the conductor-like polarizable continuum (CPCM) model. We find that the N-halogenated derivatives of amines and amides should generally cleave in such a way as to afford •NRR′ and X-. For the N-halogenated imides, on the other hand, the N-brominated derivatives are predicted to produce •Br in solution, whereas the N-chlorinated derivatives again would give Cl-. Importantly, we predict that N-bromouracil is likely to afford •Br. This may have important implications in terms of inflammatory-related diseases, because •Br may damage biomolecules such as proteins and DNA. To assist in the determination of the gas-phase EAs of larger •NRR′ radicals, not amenable to investigation using W1w, we have evaluated the performance of a wide range of lower-cost theoretical methods. Of the standard density functional theory (DFT) procedures, M06-2X, τ-HCTHh, and B3-LYP show good performance, with mean absolute deviations (MADs) from W1w of 4.8-6.8 kJ mol-1, whereas ROB2-PLYP and B2-PLYP emerge as the best of the double-hybrid DFTs (DHDFTs), with MADs of 2.5 and 3.0 kJ mol-1, respectively. Of the Gn-type procedures, G3X and G4 show very good performance (MADs = 2.4 and 2.6 kJ mol-1, respectively). The G4(MP2)-6X+ procedure performs comparably, with an MAD of 2.7 kJ mol-1, with the added advantage of significantly reduced computational expense.

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