The reactivity of a ,disilamolybdenocenophane (1) towards several unsaturated substrates has been studied. Treatment of 1 with N-heterocyclic carbene afforded an ansa-metallocene carbene complex. The cleavage of the P=S bond of a phosphane sulfide was observed, resulting in the incorporation of sulfur into the disila-bridging unit and coordination of the phosphane moiety to Mo. Reactions of 1 with carbodiimide and phosphaalkyne led to side-on coordinated products. All products were fully characterized by multinuclear NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction studies.