Spontaneous proton transfers induced by beryllium bonds

Mó, Otília; Yáñez, Manuel; Alkorta, Ibón; Elguero, José

doi:10.1080/00268976.2013.843034

Cited by 32 publications

(15 citation statements)

References 35 publications

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“…Confirming some of our results above, previous studies have shown that transfer of a proton or halogen can also be promoted by a strong beryllium bond . When the hydroxyl O atom of acetic acid is engaged in a BeB with BeCl 2 , the hydroxyl H atom forms a stronger HB, which can also lead to proton transfer if the base is strong enough . When BeH 2 approaches the hydroxyl O atom of malonaldehyde, the intramolecular HB in the latter becomes stronger, leading to a proton transfer, whereas a reverse result is obtained if the carbonyl O atom binds with BeH 2.…”

Section: Resultssupporting

confidence: 90%

“…A beryllium bond (BeB) was shown to be stronger than the corresponding MgB given the same base . Confirming some of our results above, previous studies have shown that transfer of a proton or halogen can also be promoted by a strong beryllium bond . When the hydroxyl O atom of acetic acid is engaged in a BeB with BeCl 2 , the hydroxyl H atom forms a stronger HB, which can also lead to proton transfer if the base is strong enough .…”

Section: Resultssupporting

confidence: 84%

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Effect of Magnesium Bond on the Competition Between Hydrogen and Halogen Bonds and the Induction of Proton and Halogen Transfer

Scheiner

2018

ChemPhysChem

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Section: Resultssupporting

confidence: 90%

Section: Resultssupporting

confidence: 84%

Effect of Magnesium Bond on the Competition Between Hydrogen and Halogen Bonds and the Induction of Proton and Halogen Transfer

Scheiner

2018

ChemPhysChem

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“…43,44 In the particular case of squaric acid and its derivatives, 45 a remarkable increase in acidity is observed upon complexation with beryllium difluoride, as a consequence of the electron density redistribution in the system caused by the beryllium bond formation as previously described.…”

Section: Spontaneous Loss Of H2supporting

confidence: 55%

Some Interesting Features of Non-Covalent Interactions

Martín-Sómer¹,

Montero‐Campillo²,

Mó³

et al. 2014

Croat. Chem. Acta

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Abstract. Interactions between closed-shell systems exhibit some common features, four of which are particularly strong for beryllium bonds: geometrical distortion, cooperativity, changes in intrinsic reactivity and changes in the magnetic properties of the interacting subunits, which reflect the perturbations of their electron densities through polarization effects. Structural changes lead to interaction energies that can only be adequately accounted for when the effects of the distortion on the intrinsic reactivity of the system, and not only its deformation energy, are taken into consideration. Self-assembling of ditopic systems may lead to n-mers stabilized by strong cooperative effects. Chemical shifts and coupling constants also reflect the perturbations of the electron density and accordingly cooperative effects. These four features are common to any interaction involving two closed-shell systems, one acting as Lewis acid and the other as Lewis base, and the only difference between the nature of the interactions is quantitative.

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“…The mechanism of ionization in many mass spectrometers relies on proton transfer reactions or ion attachments in the gas phase. Although a proton transfer easily occurs in solutions due to solvent mediated effects or it can be facilitated by the presence of other chemical entities such as metal salts, a spontaneous proton transfer in the gas phase is hindered because of a high energy required for the deprotonation of a proton donor that typically exceeds 250 kcal mol –1 . On the other hand, proton affinities (PA) of usual proton acceptors are lower than 250 kcal mol –1 , which reveals a thermodynamic mismatch that prevents an efficient proton transfer .…”

Section: Introductionmentioning

confidence: 99%

A density functional theory study on the superacidity of sulfuric, fluorosulfuric, and triflic acid derivatives with two cyclopentadiene rings: ion pairs formation in the gas phase

Valadbeigi

Vianello

2019

J of Physical Organic Chem

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The gas phase acidity of organosulfuric acid derivatives with two cyclopentadiene rings replacing the doubly‐bonded oxygen atoms was computationally assessed using the B3LYP DFT functional and 6–311++G(d,p) basis set. Introduced five‐membered rings increased the acidity through the delocalization of the excess negative charge in conjugates bases and by providing positions to accommodate electron withdrawing substituents such as F and CN. The calculated enthalpies of deprotonation (∆Hacid) of polycyanated systems were as low as 227.8 to 263.2 kcal mol–1 indicating exceptional superacidity. Substitution of one OH moiety by F or CF3 groups offered additional acidifying effect by preventing prototropic tautomerism in the neutral acids that acts towards lowering the acidity. The designed systems spontaneously protonated H2O and NH3 in the gas phase and produced stable ion pair clusters.

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Spontaneous proton transfers induced by beryllium bonds

Cited by 32 publications

References 35 publications

Effect of Magnesium Bond on the Competition Between Hydrogen and Halogen Bonds and the Induction of Proton and Halogen Transfer

Effect of Magnesium Bond on the Competition Between Hydrogen and Halogen Bonds and the Induction of Proton and Halogen Transfer

Some Interesting Features of Non-Covalent Interactions

A density functional theory study on the superacidity of sulfuric, fluorosulfuric, and triflic acid derivatives with two cyclopentadiene rings: ion pairs formation in the gas phase

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