Quantum chemical analysis of noncovalent bonds within crystals. Concepts and concerns

Scheiner, Steve

doi:10.1039/d3ce00708a

Cited by 2 publications

(1 citation statement)

References 103 publications

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“…The dimerization energy stands at -11.7 kcal/mol, incorporating both the SpBs and CH•••S contacts. As a first approximation [115], to isolate the contribution of SpBs, a modified dimer was analyzed where -NR 2 (R = cyclohexyl) in 3 was substituted with -NH 2 groups. This change eliminates the CH•••S contacts and other van der Waals CH•••HC interactions, lowering the interaction energy to −4.9 kcal/mol.…”

Section: Dft Calculationsmentioning

confidence: 99%

A Computational Chemistry Investigation of the Influence of Steric Bulk of Dithiocarbamato-Bound Organic Substituents upon Spodium Bonding in Three Homoleptic Mercury(II) Bis(N,N-dialkyldithiocarbamato) Compounds for Alkyl = Ethyl, Isobutyl, and Cyclohexyl

Gomila,

Tiekink,

Frontera

2023

Inorganics

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Three homoleptic Hg(S2CNR2)2, for R = ethyl (1), isobutyl (2), and cyclohexyl (3), compounds apparently exhibit a steric-dependent supramolecular association in their crystals. The small group in 1 allows for dimer formation via covalent Hg–S interactions through an eight-membered {–HgSCS}2 ring as the dithiocarbamato ligands bridge centrosymmetrically related Hg atoms; intradimer Hg···S interactions are noted. By contrast, centrosymmetrically related molecules in 2 are aligned to enable intermolecular Hg···S interactions, but the separations greatly exceed the van der Waals radii. The large group in 3 precludes both dimerization and intermolecular Hg···S interactions. Computational chemistry indicates that the potential region at the Hg atom is highly dependent on the coordination geometry about the Hg atom. Intramolecular (1) and intermolecular (2) spodium bonding (SpB) is demonstrated. Even at separations approaching 0.4 Å beyond the sum of the assumed van der Waals radii, the energy of the stabilization afforded by the structure directs SpB in 2 amounts to approximately 2.5 kcal/mol. A natural bond orbital (NBO) analysis points to the importance of the LP(S) → σ*(Hg–S) charge transfer and to the dominance of the dispersion forces and electron correlation to the SpB in 2.

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Section: Dft Calculationsmentioning

confidence: 99%

A Computational Chemistry Investigation of the Influence of Steric Bulk of Dithiocarbamato-Bound Organic Substituents upon Spodium Bonding in Three Homoleptic Mercury(II) Bis(N,N-dialkyldithiocarbamato) Compounds for Alkyl = Ethyl, Isobutyl, and Cyclohexyl

Gomila,

Tiekink,

Frontera

2023

Inorganics

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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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Quantum chemical analysis of noncovalent bonds within crystals. Concepts and concerns

Abstract: The quantum chemical calculation of the strength of a primary noncovalent bond within a crystal must navigate numerous complicating issues. Choice of geometry, polarizing effects of substituents, and delocalized interactions, must all be considered.

Cited by 2 publications

References 103 publications

A Computational Chemistry Investigation of the Influence of Steric Bulk of Dithiocarbamato-Bound Organic Substituents upon Spodium Bonding in Three Homoleptic Mercury(II) Bis(N,N-dialkyldithiocarbamato) Compounds for Alkyl = Ethyl, Isobutyl, and Cyclohexyl

A Computational Chemistry Investigation of the Influence of Steric Bulk of Dithiocarbamato-Bound Organic Substituents upon Spodium Bonding in Three Homoleptic Mercury(II) Bis(N,N-dialkyldithiocarbamato) Compounds for Alkyl = Ethyl, Isobutyl, and Cyclohexyl

Anions as Lewis Acids in Noncovalent Bonds

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