Thiolate protected metal clusters are valuable precursors for the design of tailored nanosized catalysts. Their performance can be tuned precisely at atomic level, e.g. by the configuration/ type of ligands or by partial/complete removal of the ligand shell through controlled pre-treatment steps. However, the interaction between the ligand shell and the oxide support, as well as ligand removal by oxidative pre-treatment, are still poorly understood. Typically, it was assumed that the thiolate ligands are simply converted into SO 2 , CO 2 and H 2 O. Herein, we report the first detailed observation of sulfur ligand migration from Au to the oxide support upon deposition and oxidative pre-treatment, employing mainly S K-edge XANES. Conse- quently, thiolate ligand migration not only produces clean Au cluster surfaces but also the surrounding oxide support is modified by sulfur-containing species, with pronounced effects on catalytic properties

Peer Reviewed