Sulphonylium ions in the gas phase

Chatgilialoglu, Chryssostomos; Guerra, Maurizio; Pelli, Beatrice; Traldi, Pietro

doi:10.1002/oms.1210240703

Cited by 8 publications

(5 citation statements)

References 31 publications

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“…8 should be considered from prior studies of one-electron impact mass spectrometry of aromatic sulfonyl halides. 15,32 Reactions A and B in this figure are bond cleavages of sulfur and benzene ring. Reactions C and D are bond cleavages between sulfur and halogen.…”

Section: Resultsmentioning

confidence: 99%

Preparation of Thin Cation-Exchange Membranes Using Glow Discharge Plasma Polymerization and Its Reactions

Uchimoto¹,

Endo²,

Yasuda³

et al. 2000

J. Electrochem. Soc.

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Thin cation-exchange films with fixed sulfonic acid groups were prepared by plasma polymerization followed by hydrolysis of sulfonyl halide groups using benzenesulfonyl fluoride and benzenesulfonyl chloride as starting materials. For benzenesulfonyl fluoride, sulfonyl fluoride groups were introduced into the plasma-formed polymers, whereas benzenesulfonyl chloride tended to decompose during plasma polymerization. The difference between the reaction in the glow discharge plasma of benzenesulfonyl fluoride and that of benzenesulfonyl chloride is discussed based on results obtained by in situ mass spectrometry and molecular orbital calculations. For benzenesulfonyl fluoride, the parent ion ([C 6 H 5 SO 2 F] ϩ• ) is the major species which introduces the sulfonic fluoride groups into the plasma polymer because S-F bond cleavage is difficult. However, the parent ion of benzenesulfonyl chloride is unstable in the glow discharge plasma, and cleavage of the S-Cl bond is facile and produces Cl radicals. The plasma polymer formed at 3.5 W using benzenesulfonyl fluoride exhibits a cation-exchange capacity of 1.3 mequiv g Ϫ1 after hydrolysis, which is comparable to the capacities of commercially available cation-exchange membranes.

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Section: Resultsmentioning

confidence: 99%

Preparation of Thin Cation-Exchange Membranes Using Glow Discharge Plasma Polymerization and Its Reactions

Uchimoto¹,

Endo²,

Yasuda³

et al. 2000

J. Electrochem. Soc.

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“…The adduct formed between CH 3 S • and O 2 was observed at low temperatures (−57 °C to −15 °C) and was estimated to be bound by ∼11 kJ mol -1 . Reactions of sulfinyl and sulfonyl cations were recently studied. − However, in some of these studies, direct observation of both the parent and its fragments was not feasible, and in many cases it was impossible to create and distinguish different isomers. Therefore, we used neutralization−reionization mass spectrometry (NRMS) along with high-level computational methods to address the stability and reactions of selected [C, H 3 , S, O 2 ] radicals and cations in the gas phase.…”

Section: Introductionmentioning

confidence: 99%

Methylsulfonyl and Methoxysulfinyl Radicals and Cations in the Gas Phase. A Variable-Time and Photoexcitation Neutralization−Reionization Mass Spectrometric and ab Initio/RRKM Study

Frank

Tureček

1999

J. Phys. Chem. A

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The title radicals were produced by femtosecond collisional electron transfer in the gas phase and studied by the methods of variable-time neutralization−reionization mass spectrometry combined with fast-beam laser photoexcitation and G2(MP2) ab initio/RRKM calculations. The methylsulfonyl radical (CH3SO2 •, 1) was calculated to be bound by 59 kJ mol-1 against the lowest-energy dissociation to CH3 • and SO2 at 0 K and to have a heat of formation Δ H f,298(1) = −211 ± 4 kJ mol-1. When formed by vertical electron transfer, radical 1 dissociated rapidly due to a large Franck−Condon energy, E FC = 141 kJ mol-1. The reverse addition of CH3 • to the sulfur atom in SO2 had a potential energy barrier of 1.3 kJ mol-1 and Arrhenius parameters, log A = 12.19 and E a = 5.4 kJ mol-1. The calculated addition rate constant, k 295 = 1.7 × 1011 cm3 mol-1 s-1, was in excellent agreement with the previous measurement of Simons et al. The methoxysulfinyl radical (CH3OSO•, 2) was calculated to exist as an equilibrium mixture of syn (2s) and anti (2a) conformers. The Boltzmann-averaged heat of formation of 2 was calculated as Δ H f,298(2) = −230 ± 4 kJ mol-1. Vertical neutralization of ions 2s + and 2a + produced substantial fractions of stable 2s,a. Dissociating 2s,a formed CH3 • and SO2 through unimolecular isomerization to 1. Direct dissociation of the C−O bond in 2s,a to form CH3 • and SO2 was calculated to have a large activation barrier (152 kJ mol-1 from 2a) and did not compete with the isomerization to 1, which required 111 kJ mol-1 from 2a. Photoexcitation of 2s,a resulted in a slightly increased formation of 2s,a +. This was interpreted with the help of CIS/6-311+G(3df,2p) calculations as being due to the formation of a bound excited B state of 2s upon electron transfer. The B state was photoexcited at 488 and 514.5 nm to high Rydberg states which were predicted to have large cross sections for collisional ionization. The A state of 2s was calculated to be bound but photoinactive. The C through E states of 2s were unbound and predicted to dissociate exothermically to CH3OS and (3P)O.

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“…The bond dissociation energy for MSC has been reported as 70 ± 3 kcal/mol by Chatgilialoglu et al Using this value, E avl (= h ν − BDE) for MSC is 75.8 kcal/mol. Chatgilialoglu et al . have also investigated a series of substituted sulfonyl chlorides (alkyls and aryls) and found very similar BDE values.…”

Section: Resultsmentioning

confidence: 94%

Methylsulfonyl Radical Unimolecular Dissociation Studied by Deep-UV Ultrafast Photoionization Spectroscopy

2000

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The secondary dissociation dynamics of the methylsulfonyl radical following the photodissociation near 193 nm of methylsulfonyl chloride and methylsulfonyl ethanol has been studied using femtosecond mass-resolved photoionization spectroscopy. The primary dissociation is instrument-limited (<200 fs) for both precursors. The methylsulfonyl unimolecular dissociation is measured to have a lifetime of 0.34 ps with complete secondary dissociation following methylsulfonyl chloride photolysis. For the case of methylsulfonyl ethanol, the measured lifetime is 1.1 ps and ∼40% of the radical remains undissociated for the 18 ps duration of the experiment. We have successfully modeled the experimental results assuming an impulsive dissociation process to yield the internal energy distributions in the primary photoproducts and RRKM calculations based on structures and energetics of the methylsulfonyl radical obtained from the literature.

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Sulphonylium ions in the gas phase

Cited by 8 publications

References 31 publications

Preparation of Thin Cation-Exchange Membranes Using Glow Discharge Plasma Polymerization and Its Reactions

Preparation of Thin Cation-Exchange Membranes Using Glow Discharge Plasma Polymerization and Its Reactions

Methylsulfonyl and Methoxysulfinyl Radicals and Cations in the Gas Phase. A Variable-Time and Photoexcitation Neutralization−Reionization Mass Spectrometric and ab Initio/RRKM Study

Methylsulfonyl Radical Unimolecular Dissociation Studied by Deep-UV Ultrafast Photoionization Spectroscopy

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