NO3− anions can act as Lewis acid in the solid state

Bauzá, Antonio; Frontera, Antonio; Mooibroek, Tiddo J.

doi:10.1038/ncomms14522

Cited by 83 publications

(55 citation statements)

References 38 publications

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“…No van der Waals overlap was observed, yet 36 % of the data falls within the Σ vdWaals +0.5 Å criterion. Further attempts to quantify the directionality of this interaction were inconclusive (see section 2.3 of the Supporting Information) due to the diverse steric effects of the nitro aromatic ligands and/or because there were insufficient data points …”

Section: Resultsmentioning

confidence: 99%

π‐Hole Interactions Involving Nitro Aromatic Ligands in Protein Structures

Bauzá

Mooibroek

2019

Chemistry A European J

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Studying noncanonical intermolecular interactions between a ligand and a protein constitutes an emerging research field. Identifying synthetically accessible molecular fragments that can engage in intermolecular interactions is a key objective in this area. Here, it is shown that so‐called “π‐hole interactions” are present between the nitro moiety in nitro aromatic ligands and lone pairs within protein structures (water and protein carbonyls and sulfurs). Ample structural evidence was found in a PDB analysis and computations reveal interaction energies of about −5 kcal mol−1 for ligand–protein π‐hole interactions. Several examples are highlighted for which a π‐hole interaction is implicated in the superior binding affinity or inhibition of a nitro aromatic ligand versus a similar non‐nitro analogue. The discovery that π‐hole interactions with nitro aromatics are significant within protein structures parallels the finding that halogen bonds are biologically relevant. This has implications for the interpretation of ligand–protein complexation phenomena, for example, involving the more than 50 approved drugs that contain a nitro aromatic moiety.

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Section: Resultsmentioning

confidence: 99%

π‐Hole Interactions Involving Nitro Aromatic Ligands in Protein Structures

Bauzá

Mooibroek

2019

Chemistry A European J

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“…As such, for most of the dimers, the energy due to dispersion is around 87%, while in Figure q this is only 59%. This is obviously a consequence of the involvement of the π‐hole, which is the most electropositive site and causes the interaction energy to become larger; interactions of this type involving a π‐hole have been the subject of several previous studies . Nonetheless, while the energy due to Coulombic interaction may be dominant in some systems, the importance of the quantum exchange part of the intermolecular interaction cannot be overlooked since it plays a key role in determining directionality and in explaining the equilibrium geometry of the entire chemical system.…”

Section: Discussionmentioning

confidence: 99%

Nature of halogen‐centered intermolecular interactions in crystal growth and design: Fluorine‐centered interactions in dimers in crystalline hexafluoropropylene as a prototype

Marques

Varadwaj

2019

J Comput Chem

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The wide occurrence of halogen‐centered noncovalent interactions in crystal growth and design prompted this study, which includes a mini review of recent advances in the field. Particular emphasis is placed on providing compelling theoretical evidence of the formation of these interactions between sites of positive electrostatic potential, as well as between sites of negative electrostatic potential, localized on the electrostatic surfaces of the bound fluorine atoms in a prototypical system, hexafluoropropylene (C3F6), upon its interaction with another same molecule to form (C3F6)2 dimers. The existence of σ‐ and π‐hole interactions is shown for the stable dimers. Even so, weakly bound interactions locally responsible in holding the molecular fragments together cannot and should not be overlooked since they are partly responsible for determining the overall geometry of the crystal. The results of combined quantum theory of atoms in molecules, molecular electrostatic surface potential, and reduced density gradient noncovalent interaction analyses showed that these latter interactions do indeed play a role in the stability and growth of crystalline C3F6 itself and the (C3F6)2 dimers. A symmetry adapted perturbation theory energy decomposition analysis leads to the conclusion that a great majority of the (C3F6)2 dimers examined are the consequence of dispersion (and electrostatics), with nonnegligible contribution from polarization, which together competes with an exchange repulsion component to determine the equilibrium geometries. In a few structures of the (C3F6)2 dimer, the fluorine is found to serve as a six‐center five‐bond donor/acceptor, as found for carbon in other systems (Malischewski and Seppelt, Angew. Chem. Int. Ed. 2017, 56, 368). © 2019 Wiley Periodicals, Inc.

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“…However, these contacts are most likely due to a cage effect that forces to form noncovalent interactions with appropriate cage fragments. Second, upon consideration of nucleophilic properties of positively charged metal centers one should take into account the recent finding by Bauzá, Frontera, and Mooibroek who reported an opposite phenomenon when anions such as NO 3 − in the solid state could play the role of Lewis π‐acids …”

Section: Figurementioning

confidence: 99%

Reverse Arene Sandwich Structures Based upon π‐Hole⋅⋅⋅[M^II] (d⁸ M=Pt, Pd) Interactions, where Positively Charged Metal Centers Play the Role of a Nucleophile

et al. 2019

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The complexes [Pt(tpp)] (H2tpp=tetraphenylporphyrin), [M(acac)2] (M=Pd, Pt, Hacac=acetylacetone), and [Pd(ba)2] (Hba=benzoylacetone) were co‐crystallized with highly electron‐deficient arene systems to form reverse arene sandwich structures built by π‐hole⋅⋅⋅[MII] (d8M=Pt, Pd) interactions. The adduct [Pt(tpp)]⋅2 C6F6 is monomeric, whereas the diketonate 1:1 adducts form columnar infinity 1D‐stack assembled by simultaneous action of both π‐hole⋅⋅⋅[MII] and C⋅⋅⋅F interactions. The reverse sandwiches are based on noncovalent interactions and calculated ESP distributions indicate that in π‐hole⋅⋅⋅[MII] contacts, [MII] plays the role of a nucleophile.

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NO3− anions can act as Lewis acid in the solid state

Cited by 83 publications

References 38 publications

π‐Hole Interactions Involving Nitro Aromatic Ligands in Protein Structures

π‐Hole Interactions Involving Nitro Aromatic Ligands in Protein Structures

Nature of halogen‐centered intermolecular interactions in crystal growth and design: Fluorine‐centered interactions in dimers in crystalline hexafluoropropylene as a prototype

Reverse Arene Sandwich Structures Based upon π‐Hole⋅⋅⋅[M^II] (d⁸ M=Pt, Pd) Interactions, where Positively Charged Metal Centers Play the Role of a Nucleophile

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NO3− anions can act as Lewis acid in the solid state

Cited by 83 publications

References 38 publications

π‐Hole Interactions Involving Nitro Aromatic Ligands in Protein Structures

π‐Hole Interactions Involving Nitro Aromatic Ligands in Protein Structures

Nature of halogen‐centered intermolecular interactions in crystal growth and design: Fluorine‐centered interactions in dimers in crystalline hexafluoropropylene as a prototype

Reverse Arene Sandwich Structures Based upon π‐Hole⋅⋅⋅[MII] (d8 M=Pt, Pd) Interactions, where Positively Charged Metal Centers Play the Role of a Nucleophile

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Reverse Arene Sandwich Structures Based upon π‐Hole⋅⋅⋅[M^II] (d⁸ M=Pt, Pd) Interactions, where Positively Charged Metal Centers Play the Role of a Nucleophile