The adsorption of diethyl ether (Et 2 O) on Si(001) was studied by means of scanning tunneling microscopy (STM) and photoelectron spectroscopy. Et 2 O reacts on Si(001) via a datively bonded intermediate, which was isolated at surface temperatures below 100 K. At higher surface temperature, Et 2 O converts dissociatively into the final state by cleaving one O−C bond; the resulting −O−C 2 H 5 and −C 2 H 5 fragments are found to attach on two Si dimers of neighboring dimer rows. Tipinduced hopping of the −C 2 H 5 fragment on one dimer was observed at positive sample bias. The results are discussed in the context of recent experiments on the reaction of tetrahydrofuran (THF) on Si(001) (Mette et al. ChemPhysChem 2014, 15, 3725) and allow a more general description of the reaction of ethers on Si(001).

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