Leveraging Divergent Ligand-to-Metal Charge-Transfer Excited State Pathways for Catalyst Control over Alkoxyl Radical Reactivity

-fold over the intrinsic scission of free alkoxyl radicals, highlighting the impact of accessing the excited state scission paradigm. Computations support the relevance of a scission-promoting LMCT excited state with stereoelectronically aligned alkoxyl radical cation character to enable direct, selective β-scission.