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The history of transition metal catalysis is heavily steeped in ligand design, clearly demonstrating the importance of this approach. The intimate relationship between metal and ligand can profoundly affect the outcome of a reaction, often impacting selectivity, physical properties, and the lifetime of a catalyst. Importantly, this metal-ligand relationship can provide near limitless opportunities for reaction discovery. Over the past several years, transition-metal-catalyzed C-H bond functionalization reactions have been established as a critical foundation in organic chemistry that provides new bond forming strategies. Among the d-block elements, palladium is arguably one of the most popular metals to accomplish such transformations. One possible explanation for this achievement could be the broad set of phosphine and amine based ligands available in the chemist's toolbox compatible with palladium. In parallel, other metals have been investigated for C-H bond functionalization. Among them, pentamethylcyclopentadienyl (Cp*) Rh(III) complexes have emerged as a powerful mode of catalysis for such transformations providing a broad spectrum of reactivity. This approach possesses the advantage of often very low catalyst loading, and reactions are typically performed under mild conditions allowing broad functional group tolerance. Cp*Rh(III) is considered as a privileged catalyst and a plethora of reactions involving a C-H bond cleavage event have been developed. The search for alternative cyclopentadienyl based ligands has been eclipsed by the tremendous effort devoted to exploring the considerable scope of reactions catalyzed by Cp*Rh(III) complexes, despite the potential of this strategy for enabling reactivity. Thus, ligand modification efforts in Rh(III) catalysis have been an exception and research directed toward new rhodium catalysts has been sparse. Recently, chiral cyclopentadienyl ligands have appeared allowing enantioselective Rh(III)-catalyzed C-H functionalization reactions to be performed. Alongside chiral ligands, an equally important collection of achiral cyclopentadienyl-derived ligands have also emerged. The design of this new set of ligands for rhodium has already translated to significant success in solving inherent problems of reactivity and selectivity encountered throughout the development of new Rh(III)-catalyzed transformations. This Account describes the evolution of cyclopentadienyl ligand skeletons in Rh(III)-catalysis since the introduction of pentamethylcyclopentadienyl ligands to the present. Specific emphasis is placed on reactivity and synthetic applications achieved with the new ligands with the introduction of achiral mono-, di-, or pentasubstituted cyclopentadienyl ligands exhibiting a stunning effect on reactivity and selectivity. Furthermore, an underlying question when dealing with ligand modification strategies is to explain the reason one ligand outperforms another. Conjecture and speculation abound, but extensive characterization of their steric and electronic properties has been carried out and information about electronic and steric properties of the ligands all contribute to our understanding and give crucial pieces to solve the puzzle.

Electronic and Steric Tuning of a Prototypical Piano Stool Complex: Rh(III) Catalysis for C–H Functionalization