Nitriles with exceptionally high proton affinity due to a C–N bond formation upon protonation

Valadbeigi, Younes; Causon, Tim

doi:10.1016/j.comptc.2023.114372

Cited by 2 publications

(1 citation statement)

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“…These conjugated systems continue to arouse interest as a canonical structure for strong bases design. In this regard, a few significant papers published after 2016 can be cited [ 70 , 72 , 73 , 74 , 75 , 82 , 83 , 116 , 134 , 135 , 136 , 137 , 138 , 139 , 140 , 141 ]. Note that theoretical investigations have no such difficulties as those connected with experiments.…”

Section: Overview and Prospectsmentioning

confidence: 99%

Strong Bases and beyond: The Prominent Contribution of Neutral Push–Pull Organic Molecules towards Superbases in the Gas Phase

Raczyńska,

Gal,

Maria

2024

IJMS

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In this review, the principles of gas-phase proton basicity measurements and theoretical calculations are recalled as a reminder of how the basicity PA/GB scale, based on Brønsted–Lowry theory, was constructed in the gas-phase (PA—proton affinity and/or GB—gas-phase basicity in the enthalpy and Gibbs energy scale, respectively). The origins of exceptionally strong gas-phase basicity of some organic nitrogen bases containing N-sp3 (amines), N-sp2 (imines, amidines, guanidines, polyguanides, phosphazenes), and N-sp (nitriles) are rationalized. In particular, the role of push–pull nitrogen bases in the development of the gas-phase basicity in the superbasicity region is emphasized. Some reasons for the difficulties in measurements for poly-functional nitrogen bases are highlighted. Various structural phenomena being in relation with gas-phase acid–base equilibria that should be considered in quantum-chemical calculations of PA/GB parameters are discussed. The preparation methods for strong organic push–pull bases containing a N-sp2 site of protonation are briefly reviewed. Finally, recent trends in research on neutral organic superbases, leaning toward catalytic and other remarkable applications, are underlined.

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