| Sumario: | [Fe=O(TBC)(CHCN)] (TBC = 1,4,8,1 1-tetrabenzyl-1,4,8,1 1-tetraazacyclotetradecane) is characterized, and its reactivity differences relative to O(TMC)(CHCN)] (TMC = 1,4,8,1 1-tetramethyl-1,4,8,1 1- tetraazacyclotetradecane) are evaluated in hydrogen atom (H- atom) abstraction and oxo-transfer reactions. Structural differences are defined using X-ray absorption spectroscopy and correlated to reactivities using density functional theory. The S = 1 ground states are highly similar and result in large activation barriers (~25 kcal/mol) due to steric interactions between the cyclam chelate and the substrate (e.g., ethylbenzene) associated with the equatorial it-attack required by this spin state, Conversely, H-atom abstraction reactivity on an S = 2 surface allows for a c-attack with an axial substrate approach. This results in decreased steric interactions with the cyclam and a lower barrier (~9 kcal/mol). For [Fe=O(TBC)(CHCN)], the S = 2 excited state in the reactant is lower in energy and therefore more accessible at the transition state due to a weaker ligand field associated with the steric interactions of the benzyl substituents with the trans-axial ligand. This study is further extended to the oxo-transfer reaction, which is a two-electron process requiring both a- and it-electron transfer and thus a nonlinear transition state. In oxo-transfer, the S = 2 has a lower barrier due to sequential vs concerted (S = 1) two electron transfer which gives a high-spin ferric intermediate at the transition state. The [Fe=O(TBC)(CHCN)] complex is more distorted at the transition state, with the iron farther out of the equatorial plane due to the steric interaction of the benzyl groups with the trans-axial ligand. This allows for better orbital overlap with the substrate, a lower barrier, and an increased rate of oxo-transfer.
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