High level ab initio calculations have been performed on the C-2, C-s, and C-1 conformers of S(OF)(2) using the rigorous (CCSD(T)) method for the first time. Although S(OF)(2) has not been detected experimentally, we investigate the structure, harmonic vibrational frequencies, enthalpies of reaction (Delta H-rxn degrees), and enthalpies of formation (Delta H-f degrees) for these highly reactive prototypical sulfur oxyfluorides species. These calculations have been performed with a number of extended basis sets, namely the cc-pV(T+d)Z, aug-cc-pV(T+d)Z, cc-pV(Q+d)Z, and aug-cc-pV(Q+d) Z to provide benchmark accuracy and assist in the interpretation of potential experimental work. In this report, we recommend preferred values of Delta H-f degrees for the C-2 and C-s conformers to be -74.4 and -65.6 kJ mol (1), respectively. (C) 2011 Elsevier B. V. All rights reserved.