Experimental and theoretical study of the structures and enthalpies of formation of 3 H -1,3-benzoxazole-2-thione, 3 H -1,3-benzothiazole-2-thione, and their tautomers

This paper reports an experimental and theoretical study of the structures and standard (po = 0.1 MPa) molar enthalpies of formation of 3H-1,3-benzoxazole-2-thione and 3H-1,3-benzothiazole-2-thione. The enthalpies of combustion and sublimation were measured by rotary bomb combustion calorimetry and the Knudsen effusion technique, and gas-phase enthalpies of formation values at T = 298.15 K of (42.0 ± 2.7) and (205.5 ± 3.8) kJ·mol−1 for 3H-1,3-benzoxazole-2-thione and 3H-1,3-benzothiazole-2-thione, respectively, were determined. G3-calculated enthalpies of formation are in excellent agreement with the experimental values. The present work discusses the question of tautomerism explicitly for both compounds and compares the energetics of all the related species. A comparison of the theoretical results with the structural data is also reported.The support of the Spanish Ministerio de Ciencia e Innovación under Project CTQ2007-60895/BQU and CTQ2006-10178/BQU is gratefully acknowledged. M.T. would like to thank MEC/SEUI, FPU AP2002-0603, Spain for financial support. A.V.D. thanks the National Science Foundation (CHE-0547566) and American Heart Association (0855743G) for financial support