A semiempirical study of 2,2′-dichlorodiethyl sulfide SN2 and neighboring group hydrolysis reaction mechanisms in the gas phase and in aqueous solution

Donovan, William H.; White, William E.

doi:10.1016/s0166-1280(96)04703-3

Cited by 5 publications

(6 citation statements)

References 27 publications

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“…The SES approximation has served as the basis of a number of previous investigations ,,,,,,,− of solvation effects on barriers using conventional or variational transition state theory. Some recent examples employing implicit-solvent methods are given in Table , which uses the same conventions as Table .…”

Section: 12 Ses and Esp Applicationsmentioning

confidence: 99%

Implicit Solvation Models: Equilibria, Structure, Spectra, and Dynamics

1999

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Section: 12 Ses and Esp Applicationsmentioning

confidence: 99%

Implicit Solvation Models: Equilibria, Structure, Spectra, and Dynamics

1999

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“…There is at least a dozen conformers of mustard with energies that lie within a range of 4 kcal/mol . The experimental IR and Raman spectra of mustard suggest the existence of an equilibrium mixture of conformations .…”

Section: Resultsmentioning

confidence: 99%

“…Harmonic Frequencies of the Most Stable Conformer of Sulfur Mustard. There is at least a dozen conformers of mustard with energies that lie within a range of 4 kcal/mol .…”

Section: Resultsmentioning

confidence: 99%

“…There have been few computational studies of sulfur mustard − reported to date. In a pioneering study, Bartlett et al.…”

Section: Introductionmentioning

confidence: 99%

“…The all-anti structure 1a is 2.46 kcal/mol higher in energy than 1b (Figure ) at the MP2/6-311G(d,p)//HF/6-311G(d,p) level. Two other conformations are less than one kcal/mol higher in energy than C 2 structure ( 1b ) 10a 1 The lowest energy C 2 conformation ( 1b ) of sulfur mustard optimized at the MP2(full)/6-31G(d) and B3LYP/6-311G(d,p) (values in parentheses) levels of theory. …”

Section: Introductionmentioning

confidence: 99%

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A High-Level Computational Study on the Thermochemistry and Thermal Decomposition of Sulfur Mustard (2,2‘-Dichloroethyl Sulfide): A Chemical Warfare Agent

Glukhovtsev

Bach

Nagel³

1998

J. Phys. Chem. A

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The calculations of enthalpies and free energies for various monomolecular decompositions of sulfur mustard using G2(MP2) theory have shown that noncatalytic thermal destruction of this chemical warfare agent apparently is not feasible at temperatures up to 1800 K at least. Environmentally robust decomposition/destruction demands operating conditions in excess of 2000 K to insure intrinsic safety in the absence of a catalyst. The preferable decomposition pathways involve C−C and C−S bond cleavages. The G2(MP2)-calculated enthalpy of formation of sulfur mustard is −36.86 kcal/mol for the lowest energy C 2 conformation.

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A G2 Study of SH+ Exchange Reactions Involving Lone-Pair Donors and Unsaturated Hydrocarbons

Sølling

Radom

2001

Chem. Eur. J.

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The ligand exchange reactions between mono-adducts of the sulfenium ion ([SH-X]-) and either unsaturated hydrocarbons or lone-pair donors have been investigated computationally at the G2 level. The mono-adducts react with acetylene or ethylene to form a thiiranium or a thiirenium ion, in most cases without an overall barrier. In the reactions involving lone-pair donors, the original lone-pair donor is expelled from the [SH-X]- mono-adduct with the formation of a new mono-adduct. The reaction proceeds in this case via an intermediate di-adduct. Both the hydrocarbon and the lone-pair donor attack the mono-adduct with the relevant orbitals aligned in a near-collinear fashion, as was also the case for previously investigated reactions involving PH2+ and Cl+. The reaction energies and the binding energies of the intermediate complexes in the exchange reactions are primarily determined by the electronegativities of the lone-pair donors. The thermochemical data can be rationalized within the framework of qualitative molecular orbital theory, and the results are compared with our previous findings for the corresponding reactions involving PH2+ and Cl+.

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A semiempirical study of 2,2′-dichlorodiethyl sulfide SN2 and neighboring group hydrolysis reaction mechanisms in the gas phase and in aqueous solution

Cited by 5 publications

References 27 publications

Implicit Solvation Models: Equilibria, Structure, Spectra, and Dynamics

Implicit Solvation Models: Equilibria, Structure, Spectra, and Dynamics

A High-Level Computational Study on the Thermochemistry and Thermal Decomposition of Sulfur Mustard (2,2‘-Dichloroethyl Sulfide): A Chemical Warfare Agent

A G2 Study of SH+ Exchange Reactions Involving Lone-Pair Donors and Unsaturated Hydrocarbons

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