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Issue 1, 2017
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Sizing the role of London dispersion in the dissociation of all-meta tert-butyl hexaphenylethane

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Abstract

The structure and dynamics of enigmatic hexa(3,5-di-tert-butylphenyl)ethane was characterized via NMR spectroscopy for the first time. Our variable temperature NMR analysis demonstrates an enthalpy–entropy compensation that results in a vanishingly low dissociation energy (ΔG298d = −1.60(6) kcal mol−1). An in silico study of increasingly larger all-meta alkyl substituted hexaphenylethane derivatives (Me, iPr, tBu, Cy, 1-Ad) reveals a non-intuitive correlation between increased dimer stability with increasing steric crowding. This stabilization originates from London dispersion as expressed through the increasing polarizability of the alkyl substituents. Substitution with conformationally flexible hydrocarbon moieties, e.g., cyclohexyl, introduces large unfavourable entropy contributions. Therefore, using rigid alkyl groups like tert-butyl or adamantyl as dispersion energy donors (DED) is essential to help stabilize extraordinary bonding situations.

Graphical abstract: Sizing the role of London dispersion in the dissociation of all-meta tert-butyl hexaphenylethane

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Publication details

The article was received on 21 Jun 2016, accepted on 22 Aug 2016 and first published on 23 Aug 2016


Article type: Edge Article
DOI: 10.1039/C6SC02727J
Citation: Chem. Sci., 2017,8, 405-410
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    Sizing the role of London dispersion in the dissociation of all-meta tert-butyl hexaphenylethane

    S. Rösel, C. Balestrieri and P. R. Schreiner, Chem. Sci., 2017, 8, 405
    DOI: 10.1039/C6SC02727J

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