A hexadecyl monolayer covalently attached to Si(111) surfaces (C(16)-Si(111)) was prepared at; 200 degrees C from 1-hexadecene. Formation of the monolayer was characterized by water contact all-le measurement, attenuated total reflection infrared (ATR-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Gas phase synthesized vanadium (V)-benzene (Bz) 1:2 (VBz(2)) sandwich Clusters were size-selectively deposited onto the C(16)-Si(111) substrate thus prepared and an oxidized Si substrate. Investigation of the resultant. clusters, was implemented by thermal desorption spectroscopy (TDS). About 30 K increase ill threshold desorption temperature of the landed clusters was observed oil going from the oxidized Si to the C(16)-Si(111) substrate, a, result indicating that. the clusters are more strongly bound to the C(16)-Si(111) than to the oxidized Si. This result was explained by the penetration of the landed clusters into the hexadecyl monolayer.