Molecular complexes of hydrogen halides with ethers and sulphides studied by matrix isolation vibrational spectroscopy

Barnes, Austin J.; Wright, Michael P.

doi:10.1016/0166-1280(86)80044-6

Cited by 25 publications

(8 citation statements)

References 26 publications

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“…If double acceptor configurations are in fact present in 4HBr:THF and 6HBr:THF (as suggested in the interpretation of section 3.2), then similarity of spectra suggests presence of double acceptor configurations in the “mixed” cases as well. The acid frequency in the matrix-isolated double-acceptor complex (HCl) 2 DME is 2480,8a similar to the HCl frequency in 3HCl:HBr:THF and 5HCl:HBr:THF.…”

Section: Results and Discussion: Spectra Of Amorphous And Crystallin...mentioning

confidence: 74%

Solvation Stages of HCl and HBr in Crystalline Phases with Methanol and Small Ethers: Acid−Ether Cluster Complexes in Amorphous and Crystal Phases

et al. 2004

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Solid state solvation of HCl and HBr (i.e., HX acids) was investigated by FTIR spectroscopy, with methanol (MeOH), dimethyl ether (DME), and tetrahydrofuran (THF) acting as solvents. The study is an extension of previous investigations of acid hydrates. Effort was devoted to finding those composition ratios for which the acid and the solvent readily form mixed crystalline and amorphous solids and to the study of the extent of acid solvation in these solids. The results were interpreted with the help of density functional theory (DFT) calculations for (HX) n (solvent) m clusters and for protonated solvent ions. A dramatic difference was observed between methanol and ether solvation. For methanol, crystal and amorphous ionic solids form with MeOH: HX ratios of 1:1, 2:1, and 3:1, in analogy to the hydrate case. The parallel to the HX-hydrate series apparently extends to the formation of the methanol analogues of the hydronium and Zundel cations, for the corresponding solvent-acid ratios. In contrast, mixed acid-ether solids tend to be acid-rich; new crystal solids were discovered, with HX-ether ratios of 6:1, 4:1, 2:1, and 1:1. In the limit of high acid-ether ratio, the acid is clearly molecular. In the 1:1 crystals, very intense and broad bands in the 800-1500 cm -1 range suggest proton sharing between the halide and the O atom of the ether; and a Zundel-like species [ether..H + ..X -] is suggested as the basic unit. Such units polarize, mutually solvate, and stabilize each other. In the case of HCl, the Zundel unit appears to persist to intermediate acid:ether ratios, despite dilution by the extra acid. However, in the case of 2:1 and 4:1 HBr-THF, the acid is fully molecular, though perturbed significantly by solvation.

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Section: Results and Discussion: Spectra Of Amorphous And Crystallin...mentioning

confidence: 74%

Solvation Stages of HCl and HBr in Crystalline Phases with Methanol and Small Ethers: Acid−Ether Cluster Complexes in Amorphous and Crystal Phases

et al. 2004

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“…The BSSE corrected stabilization of the PPM-B and PMM-A complex shows that they are isoenergetic and the PMM-B is the second local minimum in the potential energy surface. Table compares the shift in the experimental vibrational wavenumber with the calculated wavenumbers of the PPW-A, PWW, and PPM-A complexes computed at MP2/aug-cc-pVDZ level of theory Table S5 gives the shift in the computed wavenumber of the PPW-B, PPM-B, PMM-A, and PMM-B complexes.…”

Section: Higher Complexes Of C4h5n–h2o and C4h5n–ch3ohmentioning

confidence: 99%

“…Table 6 compares the shift in the experimental vibrational wavenumber with the calculated wavenumbers of the PPW-A, PWW, and PPM-A complexes computed at MP2/ aug-cc-pVDZ level of theory. 57 Table S5 gives the shift in the computed wavenumber of the PPW-B, PPM-B, PMM-A, and PMM-B complexes. Figure S1 shows the structure of these complexes.…”

Section: The Journal Of Physical Chemistry Amentioning

confidence: 99%

Effect of Methyl Substitution on the N–H···O Interaction in Complexes of Pyrrole with Water, Methanol, and Dimethyl Ether: Matrix Isolation Infrared Spectroscopy and ab Initio Computational Studies

2018

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Hydrogen-bonded interactions of pyrrole with water and methanol have been studied using matrix isolation infrared spectroscopy and compared with the calculation performed on dimethyl ether. Computations carried out at MP2/aug-cc-pVDZ level of theory yielded two minima for the pyrrole-water and pyrrole-methanol complexes. The global and local minima correspond to the N-H···O and O-H···π complexes, respectively, where the N-H group of pyrrole interacts with oxygen of water/methanol and O-H of water and methanol interacts with the π cloud of pyrrole. Computations performed on the pyrrole-dimethyl ether gave only N-H···O type complex. From the experimental vibrational wavenumber shifts in the N-H stretching and N-H bending modes of pyrrole, as well as in the O-H stretching modes of water and methanol, the 1:1 N-H···O complexes were discerned. The strength of the N-H···O hydrogen bond and the corresponding shift in the N-H stretching vibrational wavenumbers increases in the order pyrrole-water < pyrrole-methanol < pyrrole-dimethyl ether, where a proton is successively replaced by a methyl group. Apart from the 1:1 complexes, higher clusters of 2:1 and 1:2 pyrrole-water and pyrrole-methanol complexes were also generated in N matrix. Atoms in molecules and natural bond orbital analyses were carried out at the MP2/aug-cc-pVDZ level to understand the nature of interaction in the 1:1 pyrrole-water, pyrrole-methanol and pyrrole-dimethyl ether complexes.

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“…The abundance of structural information on the D–H···S interaction in crystallographic database of proteins and many organic molecules such as therapeutic agents, agrochemicals motivated the spectroscopic investigation of this interaction. , In terms of strength, these interactions fall within the moderate regime. Both intermolecular and intramolecular hydrogen bonding involving S and various proton donors such as H 2 O, HF, HCl, HNO 2 , HNO 3 , and CF 3 CCH in isolated matrices has been studied by several groups. − Arunan and co-workers investigated the rotational spectra of weakly bound benzene–H 2 S complex under jet cooled conditions . Biswal et al showed the existence of O–H···S hydrogen bonding interaction in gas phase using supersonic jet expansion method for the first time .…”

Section: Introductionmentioning

confidence: 99%

O–H···S Hydrogen Bonds Conform to the Acid–Base Formalism

et al. 2013

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Hydrogen bonding interaction between the ROH hydrogen bond donor and sulfur atom as an acceptor has not been as well characterized as the O-H···O interaction. The strength of O-H···O interactions for a given donor has been well documented to scale linearly with the proton affinity (PA) of the H-bond acceptor. In this regard, O-H···O interactions conform to the acid-base formalism. The importance of such correlation is to be able to estimate molecular property of the complex from the known thermodynamic data of its constituents. In this work, we investigate the properties of O-H···S interaction in the complexes of the H-bond donor and sulfur containing acceptors of varying proton affinity. The hydrogen bonded complexes of p-Fluorophenol (FP) with four different sulfur containing acceptors and their oxygen analogues, namely H2O/H2S, MeOH/MeSH, Me2O/Me2S and tetrahydrofuran (THF)/tetrahydrothiophene (THT) were characterized in regard to its S1-S0 excitation spectra and the IR spectra. Two-color resonantly enhanced multiphoton ionization (2c-R2PI), resonant ion-dip infrared (RIDIR) spectroscopy, and IR-UV hole burning spectroscopic techniques were used to probe the hydrogen bonds in the aforementioned complexes. The spectroscopic data along with the ab initio calculations were used to deduce the strength of the O-H···S hydrogen bonding interactions in these system relative to that in the O-H···O interactions. It was found that, despite being dominated by the dispersion interaction, the O-H···S interactions conform to the acid-base formalism as in the case of more conventional O-H···O interactions. The dissociation energies and the red shifts in the O-H stretching frequencies correlated very well with the proton affinity of the acceptors. However, the O-H···S interaction did not follow the same correlation as that in the O-H···O H-bond. The energy decomposition analysis showed that the dissociation energies and the red shifts in the O-H stretching frequencies follow a unified correlation if these two parameters were correlated with the sum of the charge transfer and the exchange component of the total binding energy.

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Molecular complexes of hydrogen halides with ethers and sulphides studied by matrix isolation vibrational spectroscopy

Cited by 25 publications

References 26 publications

Solvation Stages of HCl and HBr in Crystalline Phases with Methanol and Small Ethers: Acid−Ether Cluster Complexes in Amorphous and Crystal Phases

Solvation Stages of HCl and HBr in Crystalline Phases with Methanol and Small Ethers: Acid−Ether Cluster Complexes in Amorphous and Crystal Phases

Effect of Methyl Substitution on the N–H···O Interaction in Complexes of Pyrrole with Water, Methanol, and Dimethyl Ether: Matrix Isolation Infrared Spectroscopy and ab Initio Computational Studies

O–H···S Hydrogen Bonds Conform to the Acid–Base Formalism

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