Gas-phase reactivity of aluminum cluster anions with ethanethiol: Carbon-sulfur bond activation

LUO Z., SMITH J. C. , Berkdemir C., CASTLEMAN A. W.

CHEMICAL PHYSICS LETTERS, vol.590, pp.63-68, 2013 (Journal Indexed in SCI) identifier

  • Publication Type: Article / Article
  • Volume: 590
  • Publication Date: 2013
  • Doi Number: 10.1016/j.cplett.2013.10.074
  • Page Numbers: pp.63-68


We report a joint experimental and theoretical study of the gas-phase reactivity of Al cluster anions with ethanethiol (EtSH) in a fast-flow tube reactor. Nearly all Al-n(-) clusters observed are reactive at the presence of sufficient EtSH molecules with minor exceptions. Sulfide species AlnSm- dominate the observed reaction products, indicating C-S bond activation of EtSH. By using DFT calculations we provide an in-depth analysis on the interesting cluster reactivity of Al-n(-) with EtSH. It is demonstrated that the desulfurization leading to AlnSm- products is associated with the dehydrogen processes successively initiated by S-H bond cleavage and C-H bond cracking. (C) 2013 Elsevier B. V. All rights reserved.