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[en] Here we present a combined theoretical and experimental study on dissociative ionization of (η3-allyl)Ru(CO)3Br, a potential precursor for focused electron beam induced deposition. Experimental appearance energies are determined by electron impact ionization and relative cross sections for selected fragmentation channels are presented from their respective thresholds to about 70 eV incident electron energy. Threshold energies for individual fragmentation channels are computed at the hybrid density functional and coupled cluster level of theory and compared to the respective experimental appearance energies. Graphical abstract: .