Mass Spectrometric Observation of Triatomic Ions in Chlorine and Bromine Gases

Melton, Charles E.; Ropp, Gus A.; Rudolph, P. S.

doi:10.1063/1.1744637

Cited by 21 publications

(5 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Their spectroscopic feature also detected in IR and Raman spectra. Cl 3 – has been detected in gas phase using MS method . In our ESI-MS negative-ion mode, however, we did not detect the signal of the anions or any larger aggregates containing Cl 3 – or HCl 2 – .…”

Section: Resultscontrasting

confidence: 56%

“…Cl 3 À has been detected in gas phase using MS method. 46 In our ESI-MS negative-ion mode, however, we did not detect the signal of the anions or any larger aggregates containing Cl 3 À or HCl 2 À . The calculated binding energy of Cl 2 and Emim + Cl À (E b1 ; Table 2) show that, for most Emim + Cl 3 À , the E b1 is comparable with hydrogen bonds between ion pairs, such as H2ÀH5 (Table 1).…”

Section: Articlementioning

confidence: 63%

See 1 more Smart Citation

Reaction Mechanism of Cl₂ and 1-Alkyl-3-methylimidazolium Chloride Ionic Liquids

Wang

et al. 2011

J. Phys. Chem. A

View full text Add to dashboard Cite

Systems containing 1-alkyl-3-methylimidazolium chloride ionic liquid and chlorine gas were investigated. Using relativistic density functional theory, we calculated the formation mechanism of trichloride and hydrogen dichloride anions in an Emim(+)Cl(-) + Cl(2) system. Emim(+)Cl(3)(-) forms without energy barriers. The more stable species ClEmim(+)HCl(2)(-) forms through chlorine substitution. Substitution of a H on the imidazolium ring is much easier than substitution on the alkyl side chains. Infrared, Raman, ESI-MS, and (1)H NMR spectra were measured for EmimCl, BmimCl, and DmimCl with and without Cl(2) gas. The coexistence of Cl(3)(-) and HCl(2)(-), as well as chlorine-substituted cations, was confirmed by detection of their spectroscopic signals in the Cl(2) added ionic liquids. Cl substitution appears less serious for cations with longer side chains.

show abstract

Section: Resultscontrasting

confidence: 56%

Section: Articlementioning

confidence: 63%

Reaction Mechanism of Cl₂ and 1-Alkyl-3-methylimidazolium Chloride Ionic Liquids

Wang

et al. 2011

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…Detection of F 3 - in the gas phase concludes the series of nonradioactive trihalide anion observations: I 3 - (first reported in 1928 32 ), Cl 3 - (1958), and Br 3 - (1976).…”

mentioning

confidence: 75%

The First Direct Observation of the Trifluoride Anion (F₃^-) in the Gas Phase

et al. 1999

View full text Add to dashboard Cite

“…The experimental structures of these anions have been determined by spectroscopic methods. − They are linear and symmetric in the gas phase and in solution, whereas in the solid state both symmetric and asymmetric structures are found, , owing to crystal packing forces. The first trihalide anion to be detected in the gas phase was I 3 − in 1928, followed by Cl 3 − in 1958, while the gas-phase detection of Br 3 − and F 3 − was realized only one decade ago. , These species are all stable against dissociation by either exit channels, eqs and , with channel being in all cases the thermodynamically favored one. − X 3 − → X 2 + X − X 3 − → X 2 − + X • …”

Section: Introductionmentioning

confidence: 99%

Application of the Valence Bond Mixing Configuration Diagrams to Hypervalency in Trihalide Anions: A Challenge to the Rundle−Pimentel Model

Braı̈da

Hiberty

2008

J. Phys. Chem. A

View full text Add to dashboard Cite

The X(3)(-) hypercoordinated anions (H, F, Cl, Br, I) are studied by means of the breathing-orbital valence bond ab initio method. The valence bond wave functions describe the different X(3)(-) complexes in terms of only six valence bond structures and yield energies relative to the two exit channels, X(2) + X(-) and X(2)(-) + X(*), in very good agreement with reference CCSD(T) calculations. Although H(3)(-) is unstable and dissociates to H(2) + H(-), all the trihalogen anions are stable intermediates, Br(3)(-) and I(3)(-) being more stable than F(3)(-) and Cl(3)(-). As a challenge to the traditional Rundle-Pimentel model, the different energies of the hypercoordinated species relative to the normal-valent dissociation products X(2) + X(-) are interpreted in terms of valence bond configuration mixing diagrams and found to correlate with a single parameter of the X(2) molecule, its singlet-triplet energy gap. Examination of the six-structure wave functions show that H(3)(-), Cl(3)(-), Br(3)(-), and I(3)(-) share the same bonding picture and can be mainly described in terms of the interplay of two Lewis structures. On the other hand, F(3)(-) is bonded in a different way and possesses a significant three-electron bonding character that is responsible for the dissociation of this complex to F(2)(-) + F(*), instead of the more stable products F(2) + F(-). This counterintuitive preference for the thermodynamically disfavored exit channel is found to be an experimental manifestation of the large charge-shift resonance energy that generally characterizes fluorine-containing bonds.

show abstract

Mass Spectrometric Observation of Triatomic Ions in Chlorine and Bromine Gases

Cited by 21 publications

References 8 publications

Reaction Mechanism of Cl₂ and 1-Alkyl-3-methylimidazolium Chloride Ionic Liquids

Reaction Mechanism of Cl₂ and 1-Alkyl-3-methylimidazolium Chloride Ionic Liquids

The First Direct Observation of the Trifluoride Anion (F₃^-) in the Gas Phase

Application of the Valence Bond Mixing Configuration Diagrams to Hypervalency in Trihalide Anions: A Challenge to the Rundle−Pimentel Model

Contact Info

Product

Resources

About

Mass Spectrometric Observation of Triatomic Ions in Chlorine and Bromine Gases

Cited by 21 publications

References 8 publications

Reaction Mechanism of Cl2 and 1-Alkyl-3-methylimidazolium Chloride Ionic Liquids

Reaction Mechanism of Cl2 and 1-Alkyl-3-methylimidazolium Chloride Ionic Liquids

The First Direct Observation of the Trifluoride Anion (F3-) in the Gas Phase

Application of the Valence Bond Mixing Configuration Diagrams to Hypervalency in Trihalide Anions: A Challenge to the Rundle−Pimentel Model

Contact Info

Product

Resources

About

Reaction Mechanism of Cl₂ and 1-Alkyl-3-methylimidazolium Chloride Ionic Liquids

Reaction Mechanism of Cl₂ and 1-Alkyl-3-methylimidazolium Chloride Ionic Liquids

The First Direct Observation of the Trifluoride Anion (F₃^-) in the Gas Phase