title: Calorimetric and computational study of thiacyclohexane 1-oxide and thiacyclohexane 1,1-dioxide (thiane sulfoxide and thiane sulfone). Enthalpies of formation and the energy of the S=O bond.
abstract: A rotating-bomb combustion calorimeter specifically designed for the study of sulfur-containing compounds [J. Chem. Thermodyn. 1999, 31, 635] has been used for the determination of the enthalpy of formation of thiane sulfone, 4, Delta(f)H(o) m(g) = -394.8 +/- 1.5 kJ x mol(-1). This value stands in stark contrast with the enthalpy of formation reported for thiane itself, Delta(f)H(o) m(g) = -63.5 +/- 1.0 kJ x mol(-1), and gives evidence of the increased electronegativity of the sulfur atom in the sulfonyl group, which leads to significantly stronger C-SO2 bonds. Given the known enthalpy of formation of atomic oxygen in the gas phase, Delta(f)H(o) m(O,g) = +249.18 kJ x mol(-1), and the reported bond dissociation energy for the S=O bond in alkyl sulfones, BDE(S=O) = +470.0 kJ x mol(-1), it was possible to estimate the enthalpy of formation of thiane sulfoxide, 5, a hygroscopic compound not easy to use in experimental calorimetric measurements, Delta(f)H(o) m(5) = -174.0 kJ x mol(-1). The experimental enthalpy of formation of both 4 and 5 were closely reproduced by theoretical calculations at the G2(MP2)+ level, Delta(f)H(o) m(4) = -395.0 kJ x mol(-1) and Delta(f)H(o) m(5) = -178.0 kJ x mol(-1). Finally, calculated G2(MP2)+ values for the bond dissociation energy of the S=O bond in cyclic sulfoxide 5 and sulfone 4 are +363.7 and +466.2 kJ x mol(-1), respectively.
authors.affiliation: Instituto de Química Física Rocasolano, CSIC, Serrano 119, 28006 Madrid, Spain. victoriaroux@iqfr.csic.es
authors.forename: María Victoria
authors.initials: MV
authors.lastname: Roux
authors.forename: Manuel
authors.initials: M
authors.lastname: Temprado
authors.forename: Pilar
authors.initials: P
authors.lastname: Jiménez
authors.forename: Juan Zenón
authors.initials: JZ
authors.lastname: Dávalos
authors.forename: Rafael
authors.initials: R
authors.lastname: Notario
authors.forename: Ramón
authors.initials: R
authors.lastname: Guzmán-Mejía
authors.forename: Eusebio
authors.initials: E
authors.lastname: Juaristi