We have investigated the reaction of a series of acyl halides, including acetyl chloride, acetyl bromide, acetyl-d(3) chloride, benzoyl chloride, and pivaloyl chloride, on Ge(100)-2 x 1 with multiple internal reflection infrared (MIR-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). Infrared spectra following saturation exposures of acetyl chloride and acetyl bromide to Ge(100)-2 x 1 at 310 K are nearly identical, both exhibiting strong v(C=O) stretching peaks near 1685 cm(-1) and no vibrational modes in the v(Ge-H) region. These data provide strong evidence for the presence of a surface-bound acetyl group on Ge(100)-2 x 1, which results from a C-X dissociation reaction (where X = Cl, Br). For acetyl chloride, DFT calculations predict that the barrier to C-Cl dissociation is only 1 kcal/mol above a chlorine-bound precursor state and is considerably smaller than barriers leading to the [2+2] C=O cycloaddition and alpha-CH dissociation products. In addition to the C-X dissociation product, both infrared and photoelectron results point to the presence of a second structure for acetyl halides where the oxygen of the surface-bound acetyl group donates charge to a nearby surface atom. This interaction is not observed for benzoyl chloride and pivaloyl chloride.