Competition and cooperativity of hydrogen-bonding and tetrel-bonding interactions involving triethylene diamine (DABCO), H<sub>2</sub>O and CO<sub>2</sub>in air

Yang, Jianming; Yu, Qinwei; Yang, Fang-Ling; Lu, Ka; Bai, Guangdong; Dou, Wei; Yang, Lizi; Zhou, Panpan

doi:10.1039/c9nj06036g

Cited by 26 publications

(15 citation statements)

References 50 publications

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“…All calculations were carried out in the framework of the Gaussian-09 package. The M06-2X DFT functional was applied in conjunction with the aug-cc-pVDZ basis set and with the fourth-row I atom represented by the aug-cc-pVDZ-PP relativistic pseudopotential from the EMSL library. , Numerous previous studies support the accuracy and dependability of this level of theory for related sorts of noncovalent interactions. − The geometries of all species were fully optimized and verified as true minima by the presence of only positive vibrational frequencies. Interaction energies E int are defined as the difference between the energy of the complex and the sum of the two monomers of which it is comprised, holding their internal geometries as in the complex.…”

Section: Systems and Methodsmentioning

confidence: 99%

Proximity Effects of Substituents on Halogen Bond Strength

Lapp

Scheiner

2021

J. Phys. Chem. A

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It is well known that the presence of an electron-withdrawing substituent (EWS) placed near the halogen (X) atom on a Lewis acid molecule amplifies the ability of this unit to engage in a halogen bond with a base. Quantum calculations are applied to examine how quickly these effects fade as the EWS is moved further and further from the X atom. Conjugated alkene and alkyne chains of varying lengths with a terminal C−I first facilitate analysis as to how the number of these multiple bonds affects the strength of CI••N XB to NH 3 . Then, electron-withdrawing F and CN substituents are placed on the opposite end of the chain, and their effects on the XB properties are monitored as a function of their distance from I. These same EWSs are added to the ortho, meta, and para positions of aromatic iodobenzene. It is found that the XB grows in strength as more triple bonds are added to the alkyne, but there is little change caused by elongating an alkene. The cyano group has a much stronger effect than does F. While F strengthens the XB, its effects are quickly attenuated as it is moved further from I. The consequences of CN substitution are stronger and extend over a longer distance. Placement of an EWS on the phenyl ring diminishes with distance: o > m > p, and the effects of disubstitution are nearly additive. These trends apply not only to energetics but also to geometries, properties of the wave function, σ-hole depth, and NMR shielding.

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Section: Systems and Methodsmentioning

confidence: 99%

Proximity Effects of Substituents on Halogen Bond Strength

Lapp

Scheiner

2021

J. Phys. Chem. A

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“…The pseudopotential aug-cc-pVDZ-PP basis set was used for I to account for relativistic effects [31]. This level of theory has proven its accuracy and reliability for systems of this type in numerous comparisons with larger basis sets and with various levels of treatment of electron correlation [32][33][34][35][36][37][38][39][40][41][42]. The absence of imaginary frequencies in the harmonic vibrational analyses indicated that all optimized systems represent minima on their potential energy surfaces.…”

Section: Methodsmentioning

confidence: 99%

Ability of Lewis Acids with Shallow σ-Holes to Engage in Chalcogen Bonds in Different Environments

et al. 2021

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Molecules of the type XYT = Ch (T = C, Si, Ge; Ch = S, Se; X,Y = H, CH3, Cl, Br, I) contain a σ-hole along the T = Ch bond extension. This hole can engage with the N lone pair of NCH and NCCH3 so as to form a chalcogen bond. In the case of T = C, these bonds are rather weak, less than 3 kcal/mol, and are slightly weakened in acetone or water. They owe their stability to attractive electrostatic energy, supplemented by dispersion, and a much smaller polarization term. Immersion in solvent reverses the electrostatic interaction to repulsive, while amplifying the polarization energy. The σ-holes are smaller for T = Si and Ge, even negative in many cases. These Lewis acids can nonetheless engage in a weak chalcogen bond. This bond owes its stability to dispersion in the gas phase, but it is polarization that dominates in solution.

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“…Just like H-bonds, these sister interactions are also subject to cooperativity effects. ,− It is understood that the whole can be greater or less than the sum of its parts. In particular, if the central molecule B in a A··B··C triad serves as both electron donor and acceptor, the overall binding energy of this triad will be greater than the sum of the A··B and B··C binding energies in the individual dyads, i.e., positive cooperativity.…”

Section: Introductionmentioning

confidence: 99%

Competition between a Tetrel and Halogen Bond to a Common Lewis Acid

Scheiner

2020

J. Phys. Chem. A

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The T and X atoms of TF3X (T = C, Si, Ge, Sn; X = Cl, Br, I) can engage in a tetrel or halogen bond, respectively, with an approaching NH3 base. With the exception of T = C, the tetrel bonds are considerably stronger than the halogen bond regardless of the nature of T or X. Because both bonds involve electron acceptance by the central TF3X Lewis acid, there is a negative cooperativity between these two bonds when both are present. The halogen bond is weakened much more than is the tetrel bond and is in fact completely disrupted in some cases. Replacement of the three F substituents on TF3X by H attenuates the σ-holes on both T and X atoms, weakens and stretches both bonds, and eliminates any halogen bonds involving Cl. Even in those cases where a halogen bond does occur in the dimer, this bond cannot withstand the presence of a simultaneous tetrel bond and so disappears.

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Competition and cooperativity of hydrogen-bonding and tetrel-bonding interactions involving triethylene diamine (DABCO), H₂O and CO₂in air

Abstract: Triethylene diamine (DABCO) can interact with H2O and CO2 in air to form dimeric and trimeric complexes via hydrogen bond, tetrel bond as well as van der Waals interactions.

Cited by 26 publications

References 50 publications

Proximity Effects of Substituents on Halogen Bond Strength

Proximity Effects of Substituents on Halogen Bond Strength

Ability of Lewis Acids with Shallow σ-Holes to Engage in Chalcogen Bonds in Different Environments

Competition between a Tetrel and Halogen Bond to a Common Lewis Acid

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Competition and cooperativity of hydrogen-bonding and tetrel-bonding interactions involving triethylene diamine (DABCO), H2O and CO2in air

Abstract: Triethylene diamine (DABCO) can interact with H2O and CO2 in air to form dimeric and trimeric complexes via hydrogen bond, tetrel bond as well as van der Waals interactions.

Cited by 26 publications

References 50 publications

Proximity Effects of Substituents on Halogen Bond Strength

Proximity Effects of Substituents on Halogen Bond Strength

Ability of Lewis Acids with Shallow σ-Holes to Engage in Chalcogen Bonds in Different Environments

Competition between a Tetrel and Halogen Bond to a Common Lewis Acid

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Product

Resources

About

Competition and cooperativity of hydrogen-bonding and tetrel-bonding interactions involving triethylene diamine (DABCO), H₂O and CO₂in air