17O-dynamic NMR and DFT investigation of bis(acyloxy)iodoarenes.

Luca Fusaro, Francesca Mocci, Michel Luhmer, Giovanni. Cerioni

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

Bis(acetoxy)iodobenzene and related acyloxy derivs. of hypervalent I(III) were studied by variable temp. soln.-state 17O-NMR and DFT calcns. The 17O-NMR spectra reveal a dynamic process that interchanges the oxygen atoms of the acyloxy groups. For the first time, coalescence events could be detected for such compds., allowing the detn. of activation free energy data which range between 44 and 47 kJ/mol. The anal. of the 17O linewidth measured for bis(acetoxy)iodobenzene indicates that the activation entropy is negligible. DFT calcns. show that the oxygen atom exchange arises as a consequence of the [1,3]-sigmatropic shift of iodine. The calcd. activation barriers are in excellent agreement with the exptl. results. Both the 17O-NMR and DFT studies show that the solvent and chem. alterations, such as modification of the acyl groups or para-substitution of the benzene ring, hardly affect the energetics of the dynamic process. The low I-O Wiberg bond index (0.41-0.42) indicates a possible explanation of the invariance of both the energy barrier and the 17O chem. shift with para-substitution. [on SciFinder(R)]
langueAnglais
Pages12718-12733
Nombre de pages16
journalMolecules
Volume17
Les DOIs
étatPublié - 2012
Modification externeOui

Empreinte digitale

Discrete Fourier transforms
Chemical activation
Nuclear magnetic resonance
Substitution reactions
Oxygen
Atoms
Energy barriers
Interchanges
Benzene
Invariance
Coalescence
Iodine
Linewidth
Free energy
Ion exchange
Entropy
iodobenzene

mots-clés

    Citer ceci

    Fusaro, Luca ; Mocci, Francesca ; Luhmer, Michel ; Cerioni, Giovanni./ 17O-dynamic NMR and DFT investigation of bis(acyloxy)iodoarenes.Dans: Molecules. 2012 ; Vol 17. p. 12718-12733
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    abstract = "Bis(acetoxy)iodobenzene and related acyloxy derivs. of hypervalent I(III) were studied by variable temp. soln.-state 17O-NMR and DFT calcns. The 17O-NMR spectra reveal a dynamic process that interchanges the oxygen atoms of the acyloxy groups. For the first time, coalescence events could be detected for such compds., allowing the detn. of activation free energy data which range between 44 and 47 kJ/mol. The anal. of the 17O linewidth measured for bis(acetoxy)iodobenzene indicates that the activation entropy is negligible. DFT calcns. show that the oxygen atom exchange arises as a consequence of the [1,3]-sigmatropic shift of iodine. The calcd. activation barriers are in excellent agreement with the exptl. results. Both the 17O-NMR and DFT studies show that the solvent and chem. alterations, such as modification of the acyl groups or para-substitution of the benzene ring, hardly affect the energetics of the dynamic process. The low I-O Wiberg bond index (0.41-0.42) indicates a possible explanation of the invariance of both the energy barrier and the 17O chem. shift with para-substitution. [on SciFinder(R)]",
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    Fusaro, L, Mocci, F, Luhmer, M & Cerioni, G 2012, '17O-dynamic NMR and DFT investigation of bis(acyloxy)iodoarenes.' Molecules, VOL. 17, p. 12718-12733. DOI: 10.3390/molecules171112718

    17O-dynamic NMR and DFT investigation of bis(acyloxy)iodoarenes. / Fusaro, Luca; Mocci, Francesca; Luhmer, Michel; Cerioni, Giovanni.

    Dans: Molecules, Vol 17, 2012, p. 12718-12733.

    Résultats de recherche: Contribution à un journal/une revueArticle

    TY - JOUR

    T1 - 17O-dynamic NMR and DFT investigation of bis(acyloxy)iodoarenes.

    AU - Fusaro,Luca

    AU - Mocci,Francesca

    AU - Luhmer,Michel

    AU - Cerioni,Giovanni.

    N1 - M1 - Copyright (C) 2014 American Chemical Society (ACS). All Rights Reserved. CAPLUS AN 2012:1882681(Journal; Online Computer File)

    PY - 2012

    Y1 - 2012

    N2 - Bis(acetoxy)iodobenzene and related acyloxy derivs. of hypervalent I(III) were studied by variable temp. soln.-state 17O-NMR and DFT calcns. The 17O-NMR spectra reveal a dynamic process that interchanges the oxygen atoms of the acyloxy groups. For the first time, coalescence events could be detected for such compds., allowing the detn. of activation free energy data which range between 44 and 47 kJ/mol. The anal. of the 17O linewidth measured for bis(acetoxy)iodobenzene indicates that the activation entropy is negligible. DFT calcns. show that the oxygen atom exchange arises as a consequence of the [1,3]-sigmatropic shift of iodine. The calcd. activation barriers are in excellent agreement with the exptl. results. Both the 17O-NMR and DFT studies show that the solvent and chem. alterations, such as modification of the acyl groups or para-substitution of the benzene ring, hardly affect the energetics of the dynamic process. The low I-O Wiberg bond index (0.41-0.42) indicates a possible explanation of the invariance of both the energy barrier and the 17O chem. shift with para-substitution. [on SciFinder(R)]

    AB - Bis(acetoxy)iodobenzene and related acyloxy derivs. of hypervalent I(III) were studied by variable temp. soln.-state 17O-NMR and DFT calcns. The 17O-NMR spectra reveal a dynamic process that interchanges the oxygen atoms of the acyloxy groups. For the first time, coalescence events could be detected for such compds., allowing the detn. of activation free energy data which range between 44 and 47 kJ/mol. The anal. of the 17O linewidth measured for bis(acetoxy)iodobenzene indicates that the activation entropy is negligible. DFT calcns. show that the oxygen atom exchange arises as a consequence of the [1,3]-sigmatropic shift of iodine. The calcd. activation barriers are in excellent agreement with the exptl. results. Both the 17O-NMR and DFT studies show that the solvent and chem. alterations, such as modification of the acyl groups or para-substitution of the benzene ring, hardly affect the energetics of the dynamic process. The low I-O Wiberg bond index (0.41-0.42) indicates a possible explanation of the invariance of both the energy barrier and the 17O chem. shift with para-substitution. [on SciFinder(R)]

    KW - oxygen dynamic NMR DFT bisacyloxyiodoarene

    U2 - 10.3390/molecules171112718

    DO - 10.3390/molecules171112718

    M3 - Article

    VL - 17

    SP - 12718

    EP - 12733

    JO - Molecules

    T2 - Molecules

    JF - Molecules

    SN - 1431-5165

    ER -

    Fusaro L, Mocci F, Luhmer M, Cerioni G. 17O-dynamic NMR and DFT investigation of bis(acyloxy)iodoarenes. Molecules. 2012;17:12718-12733. Disponible �, DOI: 10.3390/molecules171112718