Ligand Substituents Govern the Efficiency and Mechanistic Path of Hydrogen Production with [Cp*Rh] Catalysts.

We demonstrate that [Cp*Rh] complexes bearing substituted 2,2'-bipyridyl ligands are effective hydrogen evolution catalysts (Cp*=η5 -pentamethylcyclopentadienyl). Disubstitution (at the 4 and 4' positions) of the bipyridyl ligand (namely -tBu, -H, and -CF3 ) modulates the catalytic overpotential, in part due to involvement of the reduced ligand character in formally rhodium(I) intermediates. These reduced species are synthesized and isolated here; protonation results in formation of complexes bearing the unusual η4 -pentamethylcyclopentadiene ligand, and the properties of these protonated intermediates further govern the catalytic performance. Electrochemical studies suggest that multiple mechanistic pathways are accessible, and that the operative pathway depends on the applied potential and solution conditions. Taken together, these results suggest synergy in metal-ligand cooperation that modulates the mechanisms of fuel-forming catalysis with organometallic compounds bearing multiple non-innocent ligands.