Lone pair···π interactions involving an aromatic π-system: Complexes of hexafluorobenzene with dimethyl ether and trimethylamine

Geboes, Yannick; Proft, Frank De; Herrebout, Wouter A.

doi:10.1016/j.cplett.2016.01.029

Cited by 8 publications

(3 citation statements)

References 39 publications

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“…Although the interaction described above resembles lone pair–π (or anion–π) interactions) [ 42 ], where a positive electrostatic potential region located at the center of the aromatic moiety interacts with an electron rich moiety, we (and other research groups [ 41 ]) consider this particular interaction as a σ-hole bonding. That is, the positive electrostatic potential area emerges over the center of the ring as the superposition of six/five σ-holes at the extension of the Si/Ge–Cl covalent bonds.…”

Section: Resultsmentioning

confidence: 99%

Tetrel Bonding Interactions in Perchlorinated Cyclopenta- and Cyclohexatetrelanes: A Combined DFT and CSD Study

Bauzá

2018

Molecules

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In this manuscript, we combined DFT calculations (PBE0-D3/def2-TZVP level of theory) and a Cambridge Structural Database (CSD) survey to evaluate the ability of perchlorinated cyclopenta- and cyclohexatetrelanes in establishing tetrel bonding interactions. For this purpose, we used Tr5Cl10 and Tr6Cl12 (Tr = Si and Ge) and HCN, HF, OH− and Cl− as electron donor entities. Furthermore, we performed an Atoms in Molecules (AIM) analysis to further describe and characterize the interactions studied herein. A survey of crystal structures in the CSD reveals that close contacts between Si and lone-pair-possessing atoms are quite common and oriented along the extension of the covalent bond formed by the silicon with the halogen atom.

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Section: Resultsmentioning

confidence: 99%

Tetrel Bonding Interactions in Perchlorinated Cyclopenta- and Cyclohexatetrelanes: A Combined DFT and CSD Study

Bauzá

2018

Molecules

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“…The assignment of the vibrational modes of DME(-d 6 ) and TMA(-d 9 ) observed in liquefied noble gases has been discussed in detail in previous publications 12,[26][27][28][29][30] and is not repeated here. The assignment of the vibrational modes of CH 2 FI given is based on ab initio calculations and the Raman study reported by Feller et al 31 In order to assess the presence of halogen and/or hydrogen bonded complex, the complexation shifts of the bands in the subtracted spectra are compared to those obtained from ab initio calculations, given in Tables S3 to S6 of the ESI.…”

Section: Infrared Spectroscopymentioning

confidence: 99%

Effect of Fluorination on the Competition of Halogen Bonding and Hydrogen Bonding: Complexes of Fluoroiodomethane with Dimethyl Ether and Trimethylamine

2017

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To further rationalize the competition between halogen and hydrogen bonding, a combined experimental and theoretical study on the weakly bound molecular complexes formed between the combined halogen bond/hydrogen bond donor fluoroiodomethane and the Lewis bases dimethyl ether and trimethylamine (in standard and fully deuterated form) is presented. The experimental data are obtained by recording infrared and Raman spectra of mixtures of the compounds in liquid krypton, at temperatures between 120 and 156 K. The experiments are supported by ab initio calculations at the MP2/aug-cc-pVDZ-PP level, statistical thermodynamics and Monte Carlo free energy perturbation calculations. For the mixtures containing fluoroiodomethane and dimethyl ether a hydrogen-bonded complex with an experimental complexation enthalpy of -7.0(2) kJ mol is identified. Only a single weak spectral feature is observed which can be tentatively assigned to the halogen-bonded complex. For the mixtures involving trimethylamine, both halogen- and hydrogen-bonded complexes are observed, the experimental complexation enthalpies being -12.5(1) and -9.6(2) kJ mol respectively. To evaluate the influence of fluorination on the competition between halogen and hydrogen bonding, the results obtained for fluoroiodomethane are compared with those of a previous study involving difluoroiodomethane.

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“…The lp−π interaction is an important binding mode, occurring in biomolecules − and plays a central role in stabilizing the structures of nucleic acids and proteins and modulating the recognition of protein DNA and enzyme substrates; − it has been recently reviewed in the full context of biological systems . The interaction is currently under extensive examination with a large number of studies conducted recently. ,− As in the case of the pnicogen bond, the strength of the lp−π interaction is also sensitive to substituents. For instance, the lp−π interaction of water with hexafluorobenzene (8.8 kJ/mol) is stronger than that with benzene (2.5 kJ/mol) …”

Section: Introductionmentioning

confidence: 99%

Violation of Electrostatic Rules: Shifting the Balance between Pnicogen Bonds and Lone Pair−π Interactions Tuned by Substituents

2019

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Complexes were formed by pairing ZCl 3 (Z = P, As, or Sb) with C 2 R 4 (R = H, F, or CN). The first interaction present is a pnicogen bond between the Z atom and the CC π-bond. This bond weakens as the H atoms of ethylene are replaced by electron-withdrawing F and CN, and the potential above the alkene switches from negative to positive. In the latter two cases, another set of noncovalent bonds is formed between the Cl lone pairs of ZCl 3 and the π*(CC) antibonding orbital as well as with the F or CN substituents. The growing strength of these interactions, coupled with a large dispersion energy, more than compensates for the weak pnicogen bond in C 2 (CN) 4 , with its repulsion being between areas of positive charge on each subunit, making its complexes with ZCl 3 very strong, as high as 25 kJ/mol. The pnicogen bond in C 2 F 4 is weaker than in C 2 H 4 , and its subsidiary lone pair−π bonds are weaker than in C 2 (CN) 4 , thus the complexes of this alkene with ZCl 3 are the weakest of the set.

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Lone pair···π interactions involving an aromatic π-system: Complexes of hexafluorobenzene with dimethyl ether and trimethylamine

Cited by 8 publications

References 39 publications

Tetrel Bonding Interactions in Perchlorinated Cyclopenta- and Cyclohexatetrelanes: A Combined DFT and CSD Study

Tetrel Bonding Interactions in Perchlorinated Cyclopenta- and Cyclohexatetrelanes: A Combined DFT and CSD Study

Effect of Fluorination on the Competition of Halogen Bonding and Hydrogen Bonding: Complexes of Fluoroiodomethane with Dimethyl Ether and Trimethylamine

Violation of Electrostatic Rules: Shifting the Balance between Pnicogen Bonds and Lone Pair−π Interactions Tuned by Substituents

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