We can see the effect of the linker and its coordination more directly by comparing the relative reactivity of each type of model complex. Arranging the linkers in order of increasing reactivity for ∆∆E Y and ∆∆E R2 Y , we obtain: P(c 3 ) > P(c 4 ) > N(c 3 ) > N(c 4 ). This order is reversed for ∆∆E R3 Y . The choice of linker atoms appears to have a much larger effect on reactivity than the bite angle; the gaps in ∆∆E R Y between scans with different linker atoms with the same coordination are larger than the differences in reaction energy due to the bite angle (for any choice of ligand). Focusing on the reactivity differences between the 90 • model structures at the center of the scan (though the result is qualitatively the same for each bite angle), replacing N(c 4 ) linkers with P(c 4 ) makes Reactions 1 and 2 less favorable by 18 kcal/mol and 10 kcal/mol, respectively, and Reaction 3 more favorable by 28 kcal/mol. Replacing N(c 3 ) linkers with P(c 3 ) has a similar effect on the favorability of each reaction, with Reactions 1 and 2 becoming less favorable by 21 kcal/mol and 14 kcal/mol, respectively, and Reaction 3 becoming more favorable by 35 kcal/mol. This change in reactivity seems to be mainly due to electronic effects, as N/P linkers induce significantly different rhodium and linker atomic charges, but only subtly different geometries.