We further assess the impact of the ligand bulk on reactivity by examining the Cp * -Rh-L tilt angle ϕ for the full, analog, and minimal models in Figure . In principle, this angle should act as a proxy for the amount of space available for a reactive species to interact with rhodium, with smaller angles leaving more space on the opposite side of the molecule where the reaction takes place. The tilt angle of the reactant species in each step of the cycle follows the expected trends with the species attached to the Rh center: larger values for R1, since no extra ligand is on the Rh; intermediate values for R2, where Rh(III)H is the reactant; and smaller values for R3, where Rh(III)A is the reactant. The reaction energy and title angle seem to be varying considerably for the minimal models in Figure . However, a comparison of tilt and bite angles in Figure in the SI shows that the bite angle θ varies significantly more than the corresponding tilt angle ϕ. This suggests that the change in ϕ is only due to a rearrangement of the Cp * ring when θ changes. Comparing Figures and, removing the bulky substituent groups from the ligand scaffold shifts the ϕ values close to those of the minimal models. This further indicates that the steric effects of these substituent groups is very significant. Overall, given the flexibility in orientation of the Cp * ring around the Rh center and the likely difficulty of controlling ϕ experimentally, no further examination of this feature is done for the remainder the paper.