AB-INITIO STUDY OF THE ENERGY HYPERSURFACE OF UNEVEN SULFURANES - DISSOCIATION OF HCL FROM CL-SH(OH)-CL

The MP2/6-311G(d) level of theory has been applied to answer the quest ion of how the geometry and total energy changes with respect to lengt hening of the S-Cl bond in Cl-SH(OH)-Cl. The results predict that the title compound would readily dissociate forming HCl and Cl-S(H)O. The dissociation energy is calculated at the G2(MP2) and CCSD(T)/6-311G(d) levels of theory with zero-point and basis set corrections. Our findi ng that the sulfurane structure is trapped at a high energy minimum re lative to the HCl and SH(O)Cl component molecules implies that sulfura ne synthesis from those components is energetically an uphill process.