Reactions of mass-selected Fen + cluster ions (n=1–5) with dimethyl carbonate

The reactions of mass-selected iron clusters Fen + (n=1–5) with dimethyl carbonate, (CH3O)2CO, are examined by means of Fourier-transform ion-cyclotron-resonance mass spectrometry. For the bare metal cation Fe+, loss of a methyl radical prevails which leads to the iron carbonate species FeOC(O)OCH3 +. For the corresponding Fen + clusters, this type of reaction is not observed anymore. Instead, the clusters show a strong tendency for a formal O-atom abstraction leading to the formation of the corresponding monoxide clusters FenO+ In addition, several bond activations of dimethyl carbonate are observed which markedly differ from the behavior of the mononuclear cation. Nevertheless, a mechanistic analysis implies that the initial steps are the same for bare Fe+ as well as small Fen + clusters.