Trends in the stability of covalent dative bonds with variable solvent polarity depend on the charge transfer in the Lewis electron-pair system

Lo, Rabindranath; Manna, Debashree; Miriyala, Vijay Madhav; Nachtigallová, Dana; Hobza, Pavel

doi:10.1039/d3cp03445c

“…As can be seen in Figure 1 , according to the bonding situation of the nitrogen atom, it can be determined that a N→C dative bond is formed between the nitrogen atom and the carbon atom. In previous studies, the dative bonds with significant covalent bond components were also referred to as “dative/covalent bonds”, “covalent/dative bond” or “covalent dative bonds” [ 8 , 10 , 11 , 25 ]. Therefore, we will no longer discuss the nature of N→C dative bonds in this section and instead focus on the nature of chalcogen bonds.…”

Section: Resultsmentioning

confidence: 99%

Chalcogen-Bond-Assisted Formation of the N→C Dative Bonds in the Complexes between Chalcogenadiazoles/Chalcogenatriazoles and Fullerene C60

Zhang,

Wang

2024

Molecules

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The existence of the N→C dative bonds in the complexes between N-containing molecules and fullerenes have been verified both theoretically and experimentally. However, finding stable N→C dative bonds is still a highly challenging task. In this work, we investigated computationally the N→C dative bonds in the complexes formed by fullerene C60 with 1,2,5-chalcogenadiazoles, 2,1,3-benzochalcogenadiazoles, and 1,2,4,5-chalcogenatriazoles, respectively. It was found that the N→C dative bonds are formed along with the formation of the N–Ch···C (Ch = S, Se, Te) chalcogen bonds. In the gas phase, from S-containing complexes through Se-containing complexes to Te-containing complexes, the intrinsic interaction energies become more and more negative, which indicates that the N–Ch···C chalcogen bonds can facilitate the formation of the N→C dative bonds. The intrinsic interaction energies are compensated by the large deformation energy of fullerene C60. The total interaction energies of Te-containing complexes are negative, while both total interaction energies of the S-containing complexes and Se-containing complexes are positive. This means that the N→C dative bonds in the Te-containing complexes are more easily observed in experiments in comparison with those in the S-containing complexes and Se-containing complexes. This study provides a new theoretical perspective on the experimental observation of the N→C dative bonds in complexes involving fullerenes. Further, the formation of stable N→C dative bonds in the complexes involving fullerenes can significantly change the properties of fullerenes, which will greatly simulate and expand the application range of fullerenes.

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“…[1][2][3][4][5][6] Typically, it is marginal in covalent complexes, except covalent-dative complexes. [1][2][3][4][5][6][7][8][9][10][11] While most of the neutral covalent-dative complexes, e.g. NH 3 À BH 3 , are more stable in polar solvents, charged complexes, e.g.…”

Section: Introductionmentioning

confidence: 99%

The Stability of Hydrogen‐Bonded Ion‐Pair Complex Unexpectedly Increases with Increasing Solvent Polarity

Manna,

Lo,

Vacek

et al. 2024

Angewandte Chemie

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The generally observed decrease of the electrostatic energy in the complex with increasing solvent polarity has led to the assumption that the stability of the complexes with ion‐pair hydrogen bonds decreases with increasing solvent polarity. Besides, the smaller solvent‐accessible surface area (SASA) of the complex in comparison with the isolated subsystems results in a smaller solvation energy of the latter, leading to a destabilization of the complex in the solvent compared to the gas phase. In our study, which combines Nuclear Magnetic Resonance, Infrared Spectroscopy experiments, quantum chemical calculations, and molecular dynamics (MD) simulations, we question the general validity of this statement. We demonstrate that the binding free energy of the ion‐pair hydrogen‐bonded complex between 2‐fluoropropionic acid and n‐butylamine (CH3CHFCOO‐… NH3But+) increases with increased solvent polarity. This phenomenon is rationalized by a substantial charge transfer between the subsystems that constitute the ion‐pair hydrogen‐bonded complex. This unexpected finding introduces a new perspective to our understanding of solvation dynamics, emphasizing the interplay between solvent polarity and molecular stability within hydrogen‐bonded systems.

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The Stability of Hydrogen‐Bonded Ion‐Pair Complex Unexpectedly Increases with Increasing Solvent Polarity

Manna,

Lo,

Vacek

et al. 2024

Angew Chem Int Ed

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The generally observed decrease of the electrostatic energy in the complex with increasing solvent polarity has led to the assumption that the stability of the complexes with ion‐pair hydrogen bonds decreases with increasing solvent polarity. Besides, the smaller solvent‐accessible surface area (SASA) of the complex in comparison with the isolated subsystems results in a smaller solvation energy of the latter, leading to a destabilization of the complex in the solvent compared to the gas phase. In our study, which combines Nuclear Magnetic Resonance, Infrared Spectroscopy experiments, quantum chemical calculations, and molecular dynamics (MD) simulations, we question the general validity of this statement. We demonstrate that the binding free energy of the ion‐pair hydrogen‐bonded complex between 2‐fluoropropionic acid and n‐butylamine (CH3CHFCOO‐… NH3But+) increases with increased solvent polarity. This phenomenon is rationalized by a substantial charge transfer between the subsystems that constitute the ion‐pair hydrogen‐bonded complex. This unexpected finding introduces a new perspective to our understanding of solvation dynamics, emphasizing the interplay between solvent polarity and molecular stability within hydrogen‐bonded systems.

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Trends in the stability of covalent dative bonds with variable solvent polarity depend on the charge transfer in the Lewis electron-pair system

Abstract: Depending upon the extent of charge transfer between the subsystems, the neutral dative bond complexes may stabilise or destabilise with increase in solvent polarity.

Cited by 3 publications

References 15 publications

Chalcogen-Bond-Assisted Formation of the N→C Dative Bonds in the Complexes between Chalcogenadiazoles/Chalcogenatriazoles and Fullerene C60

Chalcogen-Bond-Assisted Formation of the N→C Dative Bonds in the Complexes between Chalcogenadiazoles/Chalcogenatriazoles and Fullerene C60

The Stability of Hydrogen‐Bonded Ion‐Pair Complex Unexpectedly Increases with Increasing Solvent Polarity

The Stability of Hydrogen‐Bonded Ion‐Pair Complex Unexpectedly Increases with Increasing Solvent Polarity

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