A series of bimetallic N-heterocyclic carbene Rh(I) complexes (13, 14, 16, 18, 19, and 21) were prepared, in which two metal fragments are linked to a central organic scaffold. These complexes were investigated as catalysts for the hydroelementation of alkynes, and their efficiency as catalysts was compared to that of a series of monometallic analogues (12, 15, 17, and 20). To determine the catalyst properties that result in a cooperative, bimetallic enhancement of the reaction rate, systematic variation of the intermetallic distance and the ligand donor properties of the bimetallic complexes was explored. Two related catalyzed reactions were investigated: the dihydroalkoxylation and hydrosilylation of alkynes. Nanoparticle formation was observed during the hydrosilylation reaction using complexes 17-19.