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

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 Al n S m - 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 Al n S m - products is associated with the dehydrogen processes successively initiated by S–H bond cleavage and C–H bond cracking.