On the HCl and DCl complexes of methylenecyclopropane in liquid argon

Szostak, Roman; Herrebout, Wouter A.; Veken, B.J. van der

doi:10.1039/b004965o

Cited by 7 publications

(4 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The appearance of two weaker complex bands, one on each side of the 1:1 bands, is similar to what has been observed for other HCl complexes, ,,− where it was shown that they arise in 1:2 species in which the second HCl molecule is hydrogen-bonded to the chlorine atom of the first. Therefore, we assign these bands to a chain-type complex with stoichiometry MCP·(HCl) 2 .…”

Section: Vibrational Spectrasupporting

confidence: 83%

“…There is some debate about the extent to which these calculations account for dispersion energy 44,45 and, hence, their applicability for predicting vibrational frequencies of van der Waals complexes may be questioned. However, we have recently shown 46,47 there is an excellent correlation between complexation shifts, at the same level, calculated in the singlemolecule approach, with experimental shifts observed in liquid argon. Therefore, it appears justified to base the present assignments on such calculations.…”

Section: Theoretical Calculationsmentioning

confidence: 80%

“…In view of the very good correlation of single molecule B3LYP/6-311++G(d,p) complexation shifts with shifts observed in LAr we have observed for other complexes, 46,47 it is of interest to see if the present calculations can be used to assign the components of the isomeric doublets to the predicted isomers. To this end, in Table 3 we have compared the observed complexation shifts, in LAr and in LN 2 , with the calculated values.…”

Section: Vibrational Spectramentioning

confidence: 80%

See 2 more Smart Citations

Ab Initio and Cryospectroscopic Investigation of the Van der Waals Complexes of Methylcyclopropane with Hydrogen Chloride and Boron Trifluoride

Everaert¹,

Herrebout²,

Veken³

2001

J. Phys. Chem. A

Self Cite

View full text Add to dashboard Cite

The mid infrared spectra of methylcyclopropane-HCl and methylcyclopropane-BF 3 mixtures, dissolved in liquid argon (LAr) or liquid nitrogen (LN 2 ), have been examined. In LAr solutions, evidence was found for the formation of two different isomers of the 1:1 van der Waals complexessan asymmetric complex, in which the electron acceptor interacts with the C-C bond adjacent to the methyl group, and a symmetric complex in which the interaction occurs with the opposite C-C bond. At higher concentrations, indications were found for the formation of a chain-type 1:2 complex. In LN 2 solutions, only the two 1:1 isomers of the HCl complex have been observed. Using spectra recorded at different temperatures, the complexation enthalpy ∆H°in LAr was determined to be -9.5(4) and -8.3(3) kJ mol -1 for the symmetric and asymmetric MCP‚ HCl complexes, and -9.1(2) and -6.7(5) kJ mol -1 for the symmetric and asymmetric MCP‚BF 3 complexes, respectively. In addition, for all investigated species, full MP2/6-31+G(d,p) geometry optimizations and B3LYP/6-311++G(d,p) frequency calculations were performed, and the complexation energies were calculated at the MP2/6-311++G(3df,2pd) level. These calculations indicate that the isomers of the MCP‚HCl complex are of comparable strength, while the asymmetric MCP‚BF 3 complex is significantly less stable than its symmetric counterpart. Using Free Energy Perturbation Monte Carlo simulations to calculate the solvent influences, and using statistical thermodynamics to account for zero-point vibrational and thermal contributions, from the experimental complexation enthalpies, the complexation energies are estimated to be -15.7(8) and -16.0(9) kJ mol -1 for the symmetric and asymmetric MCP‚HCl complexes, which is in agreement with the ab initio results, and -14.0(8) and -15.3(5) kJ mol -1 for the corresponding MCP‚BF 3 species.

show abstract

Section: Vibrational Spectrasupporting

confidence: 83%

Section: Theoretical Calculationsmentioning

confidence: 80%

Section: Vibrational Spectramentioning

confidence: 80%

See 1 more Smart Citation

Ab Initio and Cryospectroscopic Investigation of the Van der Waals Complexes of Methylcyclopropane with Hydrogen Chloride and Boron Trifluoride

Everaert¹,

Herrebout²,

Veken³

2001

J. Phys. Chem. A

Self Cite

View full text Add to dashboard Cite

show abstract

“…The presence of that effect is not surprising. It has been predicted before, for instance for HCl-complexes of simple unsaturated molecules, 32,33 when a second HCl-molecule binds at the opposite side of the plane formed by the sp 2 -carbon atoms of the p-bond. The effect is easily understood as the consequence of the fact that the first hydrogen bond donor takes up some electron density from the p-system, thereby reducing the latter's ability to bind with a second donor.…”

Section: Complexation Enthalpiesmentioning

confidence: 82%

The complexes of halothane with benzene: the temperature dependent direction of the complexation shift of the aliphatic C–H stretching

Michielsen

Dom

Veken

et al. 2010

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

The formation of C-H...π bonded complexes of halothane with benzene(-d(6)) has been studied using infrared and Raman spectroscopy of solutions in liquid krypton, in supersonic jet expansions and in room temperature vapour phase. The formation of complexes with 1 ∶ 1 and 2 ∶ 1 stoichiometry was observed. The complexation enthalpy in liquid krypton for the 1 ∶ 1 complex was determined to be -9.8(2) kJ mol(-1) and the enthalpy for the addition of a second halothane molecule to the 1 ∶ 1 complex was determined at -7.0(3) kJ mol(-1). The stretching mode of the halothane C-H bond involved in the formation of the complex in the jets was observed to blue shift by 7.7(10) cm(-1). In contrast, for the solutions of liquid krypton and the room temperature measurements a small red shift was observed. Supported by ab initio calculations and Monte Carlo simulations, this shift was explained by the differences in thermal populations of the van der Waals vibrations of the complex in the different experiments.

show abstract

Infrared and Raman Measurements of Halogen Bonding in Cryogenic Solutions

Herrebout

2014

Topics in Current Chemistry

View full text Add to dashboard Cite

Because they create a weakly interacting environment which, combined with the low temperatures used, leads to small bandwidths and thus facilitates the detection of complex bands only slightly shifted from the monomer modes, solutions in liquefied inert gases have proven to be an ideal medium to study molecular complexes held together by weak and medium-strong C-X…Y (with X=I, Br, Cl and Y=O, N, S, F, Cl, π,…) halogen bonds. In this chapter, experimental setups for infrared and Raman study of cryosolutions are described, and general methodologies used to examine weakly bound molecular complexes are discussed. The methods are illustrated using data obtained for a variety of halogen-bonded complexes involving, amongst others, the trifluorohalomethanes CF3Cl, CF3Br, and CF3I, and a variety of Lewis bases. The results are compared with theoretical data obtained from ab initio calculations, and with experimental and theoretical data obtained for complexes involving weak C-H proton donors such as CHF3. Preliminary data for mixed proton donor/halogen donors such as CHClF2, CHBrF2 are also discussed.

show abstract

On the HCl and DCl complexes of methylenecyclopropane in liquid argon

Cited by 7 publications

References 27 publications

Ab Initio and Cryospectroscopic Investigation of the Van der Waals Complexes of Methylcyclopropane with Hydrogen Chloride and Boron Trifluoride

Ab Initio and Cryospectroscopic Investigation of the Van der Waals Complexes of Methylcyclopropane with Hydrogen Chloride and Boron Trifluoride

The complexes of halothane with benzene: the temperature dependent direction of the complexation shift of the aliphatic C–H stretching

Infrared and Raman Measurements of Halogen Bonding in Cryogenic Solutions

Contact Info

Product

Resources

About