The electronic structure of the two-fold bridged [1],[1]disilamolybdenocenophane has been analyzed by means of density functional theory. As predicted, the relatively high charge at the metal center and, in particular, the highly strained geometry determine a noticeable reactivity towards unsaturated organic substrates. Thus, treatment with the nonpolar reagents 2-butyne and azobenzene leads to side-on coordination of the substrate to the metal center, whereas the reaction with polar tert-butylisonitrile gives a highly unusual structural motif in the form of an ansa-carbene.