We report on the gas phase reactions of small Fe clusters (n = 2-10) with O , N O and CO in an FT-ICR mass spectrometer. Under our experimental conditions, clusters of all sizes reacted readily with O and all but the dimer reacted with N O. Only the smallest Fe clusters (n = 2-4) appeared to activate CO . For all X-O molecules (X = O, N , CO), reaction pathways were observed that include the transfer of O atoms. In addition, the reactions with O and N O were accompanied by the loss of one or two Fe atoms. Thermochemical considerations based upon the well-known X-O bond energies were used to calculate Fe -O bond dissociation energies (BDEs) for sizes n = 2-6; these amount to roughly 550 kJ mol and thus are considerably higher than the BDE of the Fe-O ion. All oxidation reactions of the Fe clusters (n = 2-6) studied in more detail were terminated by products of Fe O stoichiometry (x = 1-4). These "microoxides of iron" are not able to activate any further X-O bonds. Secondary reactions of Fe O clusters with C H , C H and NH were investigated for two selected sizes (x = 2, 3) and compared with reactions of the naked Fe clusters.
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