Nature and angular geometry of the pre-reactive complex thiirane-chlorine monofluoride from its rotational spectrum

Evans, Christopher M.; Holloway, John H.; Legon, A. C.

doi:10.1016/0009-2614(96)00340-5

Cited by 21 publications

(3 citation statements)

References 23 publications

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“…2. From Table 2, the calculated halogen-bond length d SÁÁÁX (the distance between sulfur and halogen atoms) at the MP2(full)/aug-cc-pVDZ level is in good agreement with the experimental data [45][46][47][48][49]. The halogen-bond length d SÁÁÁX for all the complexes studied are within a range from 2.529 to 3.297 Å , all of which are less than the sums of van der Waals (vdW) radii of sulfur atom and corresponding X atoms (vdW radii for S, Cl and Br are 1.80, 1.75, and 1.85 Å , respectively).…”

Section: Geometries Energies and Topology Analysissupporting

confidence: 72%

A computational study on the nature of the halogen bond between sulfides and dihalogen molecules

Zhang

Zeng

et al. 2011

Struct Chem

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The characteristics and nature of the halogen bonding in a series of BÁÁÁXY (B = H 2 S, H 2 CS, (CH 2 ) 2 S; XY = ClF, Cl 2 , BrF, BrCl, Br 2 ) complexes were analyzed by means of the quantum theory of ''atoms in molecules'' (QTAIM) and ''natural bond orbital'' (NBO) methodology at the second-order Møller-Plesset (MP2) level. Electrostatic potential, bond length, interaction energy, topological properties of the electron density, the dipole moment, and the charge transfer were investigated systematically. For the same electron donor, the interaction energies follows the BÁÁÁBrF [ BÁÁÁClF [ BÁÁÁBrCl [ BÁÁÁBr 2 [ BÁÁÁCl 2 [ BÁÁÁClBr order. For the same electron acceptor, the interaction energies increase in the sequence of H 2 S, H 2 CS, and (CH 2 ) 2 S. Topological analyses show these halogen bonding interactions belong to weak interactions with an electrostatic nature. It was found that the strength of the halogen-bonding interaction correlates well with the electrostatic potential associated with halogen atom and the amount of charge transfer from sulfides to dihalogen molecules, indicating that electrostatic interaction plays an important role in these halogen bonds. Charge transfer is also an important factor in the halogen bonds involved with dihalogen molecules.Keywords Halogen bond Á Topological analysis of electron density Á Natural bond orbital analysis Á Electrostatic interaction Á Charge transfer

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Section: Geometries Energies and Topology Analysissupporting

confidence: 72%

A computational study on the nature of the halogen bond between sulfides and dihalogen molecules

Zhang

Zeng

et al. 2011

Struct Chem

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“…The series of halogen-bonded complexes R–X···Y involving dihalogens as Lewis acids (R, X = halogen atoms; Y = Lewis base) have been extensively characterized by rotational spectroscopy. Complexes of F 2 , − Cl 2 , − Br 2 , , ClF, − and BrCl − were studied by T. Legon’s group with a series of systematically varied Lewis bases, and the results of this comprehensive series of investigations have been previously summarized . More recently, this body of work was expanded by the same group to include and compare the gas-phase rotational spectra of new molecular pairs such as ClI···Y ,,,,− and CF 3 I···Y. ,,− …”

Section: Nature Of the Halogen Bondmentioning

confidence: 99%

The Halogen Bond

et al. 2016

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The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design.

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“…. ClF dimer has been investigated experimentally by gas-phase rotational spectroscopy [111] and its characterization through the explicitly correlated coupled cluster CCSD(T)-F12b/CBS method, established a relatively large value of −55.4 kJ mol −1 for this strong intermolecular interaction, compared with an interaction energy of −32.8 kJ mol −1 for the hydrogen-bonded analogue thiirane. .…”

Section: Cooperative Effects In Unusual Thiirane Complexesmentioning

confidence: 99%

Interplay of Hydrogen, Halogen, Lithium and Beryllium Bonds in Complexes of Thiirane

McDowell

Joseph

2015

Challenges and Advances in Computational Chemistry and Physics

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Hydrogen, halogen, lithium and beryllium bonding are briefly surveyed as a prelude to a report of a computational study of the interplay between these various non-covalent interactions. Our study used model dimers and trimers involving the thiirane molecule, (CH 2 ) 2 S, complexed with small molecules like HF, ClF, BrF, LiF and BeH 2 to assess and investigate the interplay between the different noncovalent interactions. The model trimer systems show positive cooperative effects when thiirane is one of the terminal molecules, whereas a negative cooperative effect is evident when it is at the center of the trimer. The changes in selected molecular properties, including the redistribution of charge densities obtained by the natural population analysis (NPA), implemented in the natural bond orbital (NBO) procedure, and an Atoms in Molecules (AIM) topological analysis, were useful in understanding these cooperative effects. Introduction Overview of Non-Covalent InteractionsNon-covalent interactions in molecular systems is a topic of much scientific interest as it spans a number of scientific subdisciplines. They are responsible for the existence of condensed phases, for which the forces operative between interacting neutral molecules are strong enough to limit the volume of samples of a particular material but weak enough to ensure the fluidity of such materials in bulk.Such interactions are usually dominated by classical electrostatic forces, through the interaction between the permanent multipole moments of the interacting molecular species. These electrostatic forces are usually augmented by classical polarization and quantum-mechanical dispersion forces, and their long-range behavior dependent on some inverse power of their molecular separation (usually measured by the distance between the center of masses of the interacting molecules). At equilibrium

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Nature and angular geometry of the pre-reactive complex thiirane-chlorine monofluoride from its rotational spectrum

Cited by 21 publications

References 23 publications

A computational study on the nature of the halogen bond between sulfides and dihalogen molecules

A computational study on the nature of the halogen bond between sulfides and dihalogen molecules

The Halogen Bond

Interplay of Hydrogen, Halogen, Lithium and Beryllium Bonds in Complexes of Thiirane

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