Self assembling monolayers (SAMs) of organometallic thiols trans-[HS-Pd(PBu3)(2)-SH], trans-[HS-Pd (PBu3)(2)(-C, C-C6H5)] and trans, trans-[HS-Pd(PBu3)(2)(-C, C-C6H4-C6H4-C, C-Pd(PBu3)(2)-SH] on gold were obtained from the corresponding multilayers through thermally induced desorption. Temperature-dependent synchrotron radiation-induced X-ray photoelectron spectroscopy (SR-XPS) measurements were carried out on the heated multilayers during the annealing process, in order to investigate the thermal and chemical stability of the systems. SAMs of the same organometallic thiols were also obtained by rinsing the thick films with appropriate solvents. SR-XPS was used to ascertain that the molecular and electronic structure of the two series of SAMs are not influenced by the rinsing or thermal desorption process, i.e. both strategies allow for obtaining well ordered monolayers of organometallic thiols. (C) 2012 Elsevier B. V. All rights reserved.