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Reactivity of C2Cl6 and C2Cl4 Multilayers with Fe0 Atoms over FeO(111)

The interaction of Fe0 atoms with C2Cl6 and C2Cl4 multilayers over FeO(111) has been investigated using the “atom dropping” preparation technique and a combination of temperature-programmed desorption and X-ray photoelectron spectroscopy. The reactivity and reaction products are strongly dependent on the Fe0 coverage. On C2Cl6 multilayers, submonolayer Fe0 doses lead to high reactivity and primarily FeCl3 and C4Cl6, whereas multilayer Fe0 doses lead to the production of FeCl2 and C2Cl4 with much lower Fe0 reactivity. The data are consistent with a model where Fe atoms form intermediate species at low coverage, which consist of an Fe atom inserted into a C−Cl bond. When two Fe atoms react with C2Cl6, a different intermediate species is formed that produces the alternative reaction pathway and the formation of C2Cl4. Similar atom dropping experiments demonstrate that C2Cl4 is also reactive toward Fe0 atoms at low Fe0 dose, leading to the production of one FeCl2 molecule per C2Cl4 molecule reacted. At higher...