Cations brought together by hydrogen bonds: the protonated pyridine–boronic acid dimer explained

Iribarren, Íñigo; Montero‐Campillo, M. Merced; Alkorta, Ibón; Elguero, José; Quiñonero, David

doi:10.1039/c8cp07542e

Cited by 35 publications

(43 citation statements)

References 43 publications

(47 reference statements)

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“…The catalogue of metastable H‐bonded complexes of like charged ions was expanded to dications and dianions. Anion‐anion H‐bonding has recently been identified within a crystal structure, with computational confirmation, and analysis of the CSD identified protonated pyridine‐boronic acid dimers in the solid phase. Computational tools verified that a metastable complex is converted to a global minimum within a dielectric.…”

Section: Discussionmentioning

confidence: 91%

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On the Stability of Interactions between Pairs of Anions – Complexes of MCl₃⁻ (M=Be, Mg, Ca, Sr, Ba) with Pyridine and CN⁻

et al. 2020

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The ability of the central M atom of the MCl 3 À anion, with M=Be, Mg, Ca, Sr, Ba, to engage in a noncovalent bond with an approaching nucleophile is gauged by ab initio methods. The N atom of pyridine forms a M···N bond with an interaction energy between 12 and 21 kcal mol À 1 , even though the π-hole above the M atom is not necessarily positive in sign. Despite a strong Coulombic repulsion between two anions, CN À is also able to approach the M atom so as to engage in a metastable complex that is higher in energy than the individual anions. The energy barrier separating this complex from its constituent anion pair is roughly 20 kcal mol À 1 . Despite the endothermic formation reaction energy of the CN À ···MCl 3 À complex, the electron topology signals a strong interaction, more so than in pyridine···MCl 3 À with its exothermic binding energy. The dianionic complex is held together largely on the strength of interorbital interactions, thereby overcoming a repulsive electrostatic component. The latter is partially alleviated by the pyramidalization of the MCl 3 unit which makes its π-hole more positive. The complex sinks below the separate monomers in energy when the system is immersed in an aqueous medium, with a binding energy that varies from as much as 20 kcal mol À 1 for Be down to 1.2 kcal mol À 1 for Ba.[a] Dr.

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Section: Discussionmentioning

confidence: 91%

“…Considering this background, it was quite surprising when a number of reports appeared asserting that a H‐bond could be present between a pair of species of like charge . One would have presumed that the Coulombic repulsion ought to prevent the two ions from approaching one another.…”

Section: Introductionmentioning

confidence: 99%

On the Stability of Interactions between Pairs of Anions – Complexes of MCl₃⁻ (M=Be, Mg, Ca, Sr, Ba) with Pyridine and CN⁻

et al. 2020

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“…The anion‐anion repulsion imposes a large energetic barrier of around 160–180 kJ/mol which must overcome so that the complexes can be formed . This large energetic barrier has been observed in other anion‐anion interactions . The joint analysis of electrostatic potential and electron density topologies performed on neutral and charged complexes derivatives of oxoacids revealed that the stability of the complexes in the gas phase is explained by attractive forces localized in a volume situated in the HB and defined as the electrostatic attraction region .…”

Section: Introductionmentioning

confidence: 97%

Anion‐Anion Complexes Established between Aspartate Dimers

2020

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Stable dimers aspartate-aspartate have been studied in aqueous and gas phase through theoretical simulations. The polarizable continuum model (PCM) has been applied to simulate the effect of the hydration on monomers and complexes. The quantum theory of atoms in molecules (QTAIM) and the interacting quantum atoms (IQA) scheme has been used to inquire into if, in the aqueous phase, individual hydrogen bonds have attractive electrostatic components. In all cases a spontaneous formation of the complexes in the aqueous phase are observed, while in the gas phase a considerable energy barrier must be overcome (between 100.8 to 263.2 kJ mol À 1 ). The intermolecular distance at which this barrier is indicates when the hydrogenbond interactions begin to take importance between the dimers and the corresponding molecular recognition among them. The IQA analysis shows that in aqueous phase, the hydrogen bonds NÀ H···O are mainly electrostatic in nature with a certain covalent character which increases linearly with the decrease of internuclear distances H···O. The H···H interactions observed are stabilizing and they are mainly quantum in nature.

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“…[37][38][39] The latter interaction was named as antielectrostatic interaction [40] and it was a subject of controversies and debates. [41][42][43][44] However these systems in spite they correspond to energetic minima they are characterized by positive binding energies. [44] The complexes considered here correspond to energetic minima; and additionally both {F 11 } À H + + {Y} + !…”

Section: Discussionmentioning

confidence: 99%

“…[41][42][43][44] However these systems in spite they correspond to energetic minima they are characterized by positive binding energies. [44] The complexes considered here correspond to energetic minima; and additionally both {F 11 } À H + + {Y} + ! {F 11 } À ···H + ···{Y} + and {F 11 } À + H + {Y} + !…”

Section: Discussionmentioning

confidence: 99%

Tetravalent Oxygen and Sulphur Centres Mediated by Carborane Superacid: Theoretical Analysis

et al. 2019

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The tetravalent oxygen or sulphur centres, especially in H4O2+ and H4S2+ dications, were analysed experimentally and theoretically in various studies. Herein, we discuss stabilities of such centres in related H(CH3)3O2+ and H(CH3)3S2+ dications mediated by carborane superacid. The ωB97X‐D/6‐311++G(d,p) calculations were performed for a gas phase and for different solvents characterized by a wide range of dielectric constants for complexes of these dications with the conjugated base of H(CHB11F11) carborane superacid, CHB11F11−, which indicate that these complexes are linked by hydrogen bonds. The Quantum Theory of ‘Atoms in Molecules’ (QTAIM) approach is applied to characterize these interactions. DFT results show that tetravalent oxygen and sulphur structures are additionally stabilized by polar solvents.

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Cations brought together by hydrogen bonds: the protonated pyridine–boronic acid dimer explained

Abstract: Stable dimers of protonated pyridine–boronic acid are found in the gas phase and solvent models. The importance of electrostatics is discussed.

Cited by 35 publications

References 43 publications

On the Stability of Interactions between Pairs of Anions – Complexes of MCl₃⁻ (M=Be, Mg, Ca, Sr, Ba) with Pyridine and CN⁻

On the Stability of Interactions between Pairs of Anions – Complexes of MCl₃⁻ (M=Be, Mg, Ca, Sr, Ba) with Pyridine and CN⁻

Anion‐Anion Complexes Established between Aspartate Dimers

Tetravalent Oxygen and Sulphur Centres Mediated by Carborane Superacid: Theoretical Analysis

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Cations brought together by hydrogen bonds: the protonated pyridine–boronic acid dimer explained

Abstract: Stable dimers of protonated pyridine–boronic acid are found in the gas phase and solvent models. The importance of electrostatics is discussed.

Cited by 35 publications

References 43 publications

On the Stability of Interactions between Pairs of Anions – Complexes of MCl3− (M=Be, Mg, Ca, Sr, Ba) with Pyridine and CN−

On the Stability of Interactions between Pairs of Anions – Complexes of MCl3− (M=Be, Mg, Ca, Sr, Ba) with Pyridine and CN−

Anion‐Anion Complexes Established between Aspartate Dimers

Tetravalent Oxygen and Sulphur Centres Mediated by Carborane Superacid: Theoretical Analysis

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On the Stability of Interactions between Pairs of Anions – Complexes of MCl₃⁻ (M=Be, Mg, Ca, Sr, Ba) with Pyridine and CN⁻

On the Stability of Interactions between Pairs of Anions – Complexes of MCl₃⁻ (M=Be, Mg, Ca, Sr, Ba) with Pyridine and CN⁻