Calorimetric and computational study of 1,4-dithiacyclohexane 1,1-dioxide (1,4-dithiane sulfone).
This work reports the enthalpies of formation in the condensed and gas state of 1,4-dithiacyclohexane 1,1-dioxide (1,4-dithiane sulfone, 5), derived from the enthalpy of combustion in oxygen, measured by a rotating bomb calorimeter and the variation of vapor pressures with temperatures determined by the Knudsen effusion technique. The theoretically estimated enthalpy of formation was calculated from high-level ab initio molecular orbital calculations at the G2(MP2) level. The theoretical calculations appear to be in very good agreement with experiment. A comparison of the conversion of thiane sulfone 3 to 1,3-dithiane sulfone 4 and 1,4-dithiane sulfone 5 clearly shows the 1,3 isomer to be 6.7 kJ mol(-1) less stable, probably owing to diminished electrostatic repulsion between the sulfur heteroatoms in 1,4-sulfone 5.
Roux
María Victoria
MV
Instituto de Química Física Rocasolano, CSIC, Serrano 119, 28006 Madrid, Spain.
Temprado
Manuel
M
Jiménez
Pilar
P
Notario
Rafael
R
Guzman-Mejía
Ramón
R
Juaristi
Eusebio
E
D002151:Calorimetry / Q000379:methods; D003198:Computer Simulation; D003510:Cyclohexanes / Q000138:chemical synthesis / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D010087:Oxides / Q000138:chemical synthesis / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D011312:Pressure; D012680:Sensitivity and Specificity; D013696:Temperature
C516085:1,4-dithiacyclohexane 1,1-dioxide; D003510:Cyclohexanes; D010087:Oxides; D010100:Oxygen