biostudies-literatureUnknownDreher TUniversity of YorkRoyal SocietyEngineering and Physical Sciences Research CouncilSystems incorporating the <i>cis</i>-Mo(O)₂ motif catalyse a range of important thermal homogeneous and heterogeneous oxygen atom transfer (OAT) reactions spanning biological oxidations to platform chemical synthesis. Analogous light-driven processes could offer a more sustainable approach. The <i>cis</i>-Mo(O)₂ complexes reported here photocatalyse OAT under visible light irradiation, and operate <i>via</i> a non-emissive excited state with substantial ligand-to-metal charge-transfer (LMCT) character, in which a Mo[double bond, length as m-dash]O π*-orbital is populated <i>via</i> transfer of electron density from a chromophoric salicylidene-aminophenol (SAP) ligand. SAP ligands can be prepared from affordable commercially-available precursors. The respective <i>cis<Chemical sciencehttps://www.ebi.ac.uk/biostudies/studies/S-EPMC11396016biostudies-literatureLigand-to-metal charge transfer facilitates photocatalytic oxygen atom transfer (OAT) with <i>cis</i>-dioxo molybdenum(vi)-Schiff base complexes.PMC11396016INF\R1\221057EP/T518025/1EP/T007338/1Steinfeld SDouthwaite REDreher TWhitwood ACDuhme-Klair AKGeciauskas LProcacci BLynam JMfalseLigand-to-metal charge transfer facilitates photocatalytic oxygen atom transfer (OAT) with <i>cis</i>-dioxo molybdenum(vi)-Schiff base complexes.Systems incorporating the <i>cis</i>-Mo(O)₂ motif catalyse a range of important thermal homogeneous and heterogeneous oxygen atom transfer (OAT) reactions spanning biological oxidations to platform chemical synthesis. Analogous light-driven processes could offer a more sustainable approach. The <i>cis</i>-Mo(O)₂ complexes reported here photocatalyse OAT under visible light irradiation, and operate <i>via</i> a non-emissive excited state with substantial ligand-to-metal charge-transfer (LMCT) character, in which a Mo[double bond, length as m-dash]O π*-orbital is populated <i>via</i> transfer of electron density from a chromophoric salicylidene-aminophenol (SAP) ligand. SAP ligands can be prepared from affordable commercially-available precursors. The respective <i>cis<2024-01-01T00:00:00Z2024 Sep2025-04-04T02:36:11.001Z2025-04-04T02:36:11.001ZS-EPMC113960163928264910.1039/d4sc02784a