Hydrogen Bonds Are Never of an “Anti-electrostatic” Nature: A Brief Tour of a Misleading Nomenclature

Martín-Fernández, Carlos; Montero-Campillo, M. Merced; Alkorta, Ibon

doi:10.1021/acs.jpclett.4c00779

J. Phys. Chem. Lett.

2024

DOI: 10.1021/acs.jpclett.4c00779

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Hydrogen Bonds Are Never of an “Anti-electrostatic” Nature: A Brief Tour of a Misleading Nomenclature

Carlos Martín-Fernández,

M. Merced Montero-Campillo,

Ibon Alkorta

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Cited by 4 publications

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Anions as Lewis Acids in Noncovalent Bonds

Scheiner

2024

Chemistry A European J

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The ability of an anion to serve as electron‐accepting Lewis acid in a noncovalent bond is assessed via DFT calculations. NH3 is taken as the common base, and is paired with a host of ACln‐ anions, with central atom A = Ca, Sr, Mg, Te, Sb, Hg, Zn, Ag, Ga, Ti, Sn, I, and B. Each anion reacts through its σ or π‐hole although the electrostatic potential of this hole is quite negative in most cases. Despite the contact between this negative hole and the negative region of the approaching nucleophile, the electrostatic component of the interaction energy of each bond is highly favorable, and accounts for more than half of the total attractive energy. The double negative charge of dianions precludes a stable complex with NH3.

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Anions as Lewis Acids in Noncovalent Bonds

Scheiner

2024

Chemistry A European J

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Monohydrides of the Group 13 Elements M=B, Al and Ga: Axial Bi‐Nucleophilicity and the Propensity to Form Both H−M⋅⋅⋅HX and M−H⋅⋅⋅HX Hydrogen Bonds (X=F, Cl, Br, I, CN, CCH, CP)

Alkorta,

Legon

2024

ChemPlusChem

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Equilibrium dissociation energies De of the hydrogen‐bonded complexes HAl···HX and HGa···HX (X = F, Cl, Br, I, CN, CCH, and CP) were calculated ab initio at the CCSD(T)‐(F12c)/ cc‐pVDZ‐F12 level of theory. The gradients of graphs of De versus the electrophilicity EHX of the Lewis acids HX yielded the nucleophilicities NM‐X of the Group 13 atoms M in these diatomic molecules. Molecular electrostatic surfaces potentials reveal that H‐Al and H‐Ga are bi‐nucleophilic and that the H ends of these H‐M molecules are more nucleophilic than the M ends for M = Al and Ga, but not when M = boron. Therefore, the complexes M‐H···HX were investigated using the same approach. It was concluded for M =Al and Ga that, for a given X, the M‐H···HX complexes were more strongly bound than the corresponding H‐M···HX complexes for both M = Al and Ga but the reverse order applies for M = boron. The effects of substituting the H atoms in the M‐H molecules by F atoms and by methyl groups were investigated to measure the ‐I and +I inductive effects relative to H, respectively, on the nucleophilicities of the molecules M‐H when M is acting as hydrogen‐bond acceptor in complexes H‐M···H‐X.

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IUPAC Recommendations: (Un)equivocal Understanding of Hydrogen and Halogen Bonds and Their (Un)equivocal Naming!

Arunan,

Metrangolo,

Resnati

et al. 2024

Crystal Growth & Design

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This manuscript shows that Si-H hydrogen acts as a donor of electron density to halogen atoms in Me 3 Si-H•••Y complexes (Y = CF 3 I, BrCN), thus proving that, consistent with IUPAC definitions of hydrogen and halogen bonds, hydridic hydrogen functions as a halogen bond acceptor. This has been necessitated by a paper recently published asking whether the definition of hydrogen bonding should be revised to include hydridic H atoms acting as electron donors. We discuss the various nomenclatures used for referring to intermolecular/noncovalent bonds formed by various elements and point out the convention established in naming them by IUPAC, after long deliberations among the chemists from all over the world.

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Hydrogen Bonds Are Never of an “Anti-electrostatic” Nature: A Brief Tour of a Misleading Nomenclature

Cited by 4 publications

References 92 publications

Anions as Lewis Acids in Noncovalent Bonds

Anions as Lewis Acids in Noncovalent Bonds

Monohydrides of the Group 13 Elements M=B, Al and Ga: Axial Bi‐Nucleophilicity and the Propensity to Form Both H−M⋅⋅⋅HX and M−H⋅⋅⋅HX Hydrogen Bonds (X=F, Cl, Br, I, CN, CCH, CP)

IUPAC Recommendations: (Un)equivocal Understanding of Hydrogen and Halogen Bonds and Their (Un)equivocal Naming!

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