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2004
Decomposition reactions
H 2500
The Thermal Decomposition of S2O Forming SO2, S3, S4 and S5O — An ab initio
Study. — All chemically reasonable [2+2] and [2+3] dipolar addition reactions
44- 022 MO
between two S2O molecules forming heterocyclic intermediates of composition S4O2,
as well as the decomposition of these species to generate the observed products S3 and
SO2, are studied by gas-phase ab initio MO calculations at the G3X(MP2) level of
theory. The [2+2] cycloadditions are all endothermic and are characterized by high barriers. The reaction of lowest activation enthalpy is the exothermic [2+3] cycloaddition
of two S2O molecules resulting in the five-membered heterocycle S4O2, which is predicted to decompose at 298 K exothermically to SO2 and S3. The S3 molecule is predicted to add exothermically to S2O to give homocyclic S 5O. The bimolecular decomposition of S5O to SO2, S4, and S5 is also exothermic and may explain the formation of
the red S4 molecule on condensation of S2O at temperatures below -130 °C. —
(STEUDEL*, R.; STEUDEL, Y.; Eur. J. Inorg. Chem. 2004, 17, 3513-3521; Inst.
Chem., TU Berlin, D-10623 Berlin, Germany; Eng.) — Schramke
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