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Issue 18, 2016
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Pressure-preferred symmetric reactions of 4,4′-bipyridine hydrobromide

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Abstract

High pressure and temperature trigger symmetric chemical reactions of 4,4′-bipyridine hydrobromide monohydrate (44′biPyHBr·H2O) in methanol solution. Above 0.1 GPa and 423 K, the 4,4′-bipyridinium dibromide salt (44′biPy2HBr) precipitates, while the 4,4′-bipyridine free base remains dissolved in the methanol–water mixture. At 0.35 GPa and 473 K, both pyridine moieties are N-methylated and N,N-dimethylbipyridinium dibromide (44′biPy2CH3Br) is formed. None of the high-pressure compounds of 44′biPy2HBr and 44′bPy2CH3Br are solvated, which contrasts with the strong preference of analogous 1,4-diazabicyclo[2.2.2]octane (dabco) monosalts and disalts to form solvates at high-pressure. The high-pressure reactivity of 44′biPyHBr is analogous to that of 1,4-diazabicyclo[2.2.2]octane hydrobromide (dabcoHBr); however, dabcoHBr is asymmetrically N-methylated at one amine site only. This asymmetric mono N-methylation of dabcoHBr has been associated with strong electrostatic interactions between the transannular N-atoms.

Graphical abstract: Pressure-preferred symmetric reactions of 4,4′-bipyridine hydrobromide

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Publication details

The article was received on 11 Feb 2016, accepted on 18 Mar 2016 and first published on 25 Mar 2016


Article type: Paper
DOI: 10.1039/C6CE00356G
Citation: CrystEngComm, 2016,18, 3223-3228
  • Open access: Creative Commons BY license
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    Pressure-preferred symmetric reactions of 4,4′-bipyridine hydrobromide

    M. Anioła and A. Katrusiak, CrystEngComm, 2016, 18, 3223
    DOI: 10.1039/C6CE00356G

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