Presentation Date: Feb 14, 2026
AGSA Abstract
Light hydrocarbons are the main components of petroleum and natural gas reserves and are common industrial byproducts; however, they have minimal commercial value. The development of new methodologies for the C–C bond transformation of these important yet inert synthons has garnered significant interest, influencing the synthesis of impactful compounds ranging from petrochemicals to pharmaceuticals to polymers. They are rarely employed directly as commodity precursors since they are primarily alkanes with inert C–H bonds. Industrially, C–H bond functionalization requires high temperatures and pressures. Although traditional high-valent late transition metal oxos afford intermediate metal hydroxyl compounds that remain reactive, they still direct the product scope of these reactions toward the formation of alcohols only. In recent studies, the Chambers group has utilized stable early transition Mo(VI) oxo motifs, which can be activated by 365 nm irradiation to initiate novel reactivity and yield new C–C bonds via homocoupling of unactivated substrates. This light-driven pathway also provides a strategy to directly utilize solar energy to drive chemical reactivity under benign temperature and pressure reaction conditions. Nevertheless, we are interested in understanding how synthetic modifications influence light absorption towards preparing visible light-absorbing photocatalysts. In developing visible light-absorbing photocatalysts, the Chambers group observed that simple modifications of the bpy ligand in MoO2Cl2(bpy-tBu) (where bpy-tBu is 4,4’-tert-butyl-2,2’-bipyridine) have been unsuccessful because the 4,4’ variations have little effect due to an orbital node in the HOMO. Furthermore, electron-donating groups at the 5,5’ position provide visible light absorption; however, because of ligand decomposition, they weaken the oxidation potential, inhibiting C–H activation. Additionally, a scaling relationship was noted when tuning the ancillary ligand: an increase in the energy of the anionic ligand raises the energy of the d-orbitals. Alternatively, in this work, we predicted that incorporating an extended π system or conjugation into the ligands of the primary molybdenum dioxo
