[Cp*Rh] complexes (Cp* = pentamethylcyclopentadienyl) bearing diimine type ancillary ligands have been known for some time to function as proton reduction catalysts. However, recent studies have revealed formation of unique [Cp*H] complexes after transfer of a substrate proton to the [Cp*] ligand, rather than generation of stable rhodium hydrides. Various studies have shown impact of the diimine ligand on properties of the catalyst. More recently, we have been studying the effects of varying the substitution pattern on the cyclopentadienyl-type ligand. We have substituted one methyl group of the [Cp*] ligand with a n-propyl group and a simple proton, preparing and isolating four new complexes: [(C5Me4Pr)Rh(bpy)Cl]Cl, (C5Me4Pr)Rh(bpy), [(C5Me4)Rh(bpy)Cl]Cl, and (C5Me4)Rh(bpy) (bpy = 2,2'-bipyridyl). These new complexes have similar properties to their [Cp*] analogues, but behave distinctly different after protonation. Recent results from this work will be discussed, including spectroscopic data as well as results from electrocatalytic studies of H2 generation.

Formation and reactivity of substituted η4-cyclopentadiene (Cp*H) complexes of rhodium

2019 Spring National Meeting

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