Adsorbate thermodynamics as a determinant of reaction mechanism: pentamethYlene sulfide on Mo(110)

The reactions of the totally unstrained, six-membered cyclic sulfide pentamethylene sulfide on Mo(110) have been investigated by using temperature-programmed reaction spectroscopy and X-ray photoelectron spectroscopy in an effort to identify the roles of ring size and strain in dictating reaction selectivity. Four gases products are detected in the temperature-programmed reaction of pentamethylene sulfide: dihydrogen at 380 and 590 K, pentane at 350 K, pentene at 345 K, and pentamethylene sulfide at 190 and 280 K. The kinetics for hydrocarbon production from pentamethylene sulfide are qualitatively different than for the four- and five-membered cyclic sulfides, trimethylene sulfide and tetrahydrothiophene.