We have studied the interaction of vapor-deposited Al, Cu, Ag, and Au atoms on a methoxy-terminated self-assembled monolayer (SAM) of HS(CH2)(16)OCH3 on polycrystalline Au{111}. Time-of-flight secondary ion mass spectrometry, infrared reflection spectroscopy, and X-ray photoelectron spectroscopy measurements at increasing coverages of metal show that for Cu and Ag deposition at all coverages the metal atoms continuously partition into competitive pathways: penetration through the SAM to the S/substrate interface and solvation-like interaction with the -OCH3 terminal groups. Deposited Au atoms, however, undergo only continuous penetration, even at high coverages, leaving the SAM "floating" on the Au surface. These results contrast with earlier investigations of Al deposition on a methyl-terminated SAM where metal atom penetration to the Au/S interface ceases abruptly after a similar to1:1 Al/Au layer has been attained. These observations are interpreted in terms of a thermally activated penetration mechanism involving dynamic formation of diffusion channels in the SAM via hopping of alkanethiolate-metal (RSM-) moieties across the surface. Using supporting quantum chemical calculations, we rationalized the results in terms of the relative heights of the hopping barriers, RSAI > RSAg, RSCu > RSAu, and the magnitudes of the metal-OCH3 solvation energies.