This is a really nice example of selectivity emerging from constraint, not just energetics. The Co–O–C interaction looks less like a secondary stabilisation and more like a geometric gate in configuration space, effectively collapsing the accessible pathways so the Z-product becomes the only coherent reconstruction. In that light, the DFT isn’t just explaining selectivity after the fact; it’s revealing a structure-first control mechanism, where redox mediation and MS-PCET act to maintain the constraint rather than drive the outcome. That’s an interesting direction for thinking about scalability and robustness in catalytic design. @derosalab @uclachem @ACSCatalysis