Unveiling Non-Covalent Interactions in Novel Cooperative Photoredox Systems for Efficient Alkene Oxidation in Water

A new cooperative photoredox catalytic system, [Ru^II(trpy)(bpy)(H₂O)][3,3'-Co(8,9,12-Cl₃-1,2-C₂B₉H₈)₂]₂, 5, has been synthesized and fully characterized for the first time. In this system, the photoredox catalyst [3,3'-Co(8,9,12-Cl₃-1,2-C₂B₉H₈)₂]^-[Cl^-, a metallacarborane, and the oxidation catalyst [Ru^II(trpy)(bpy)(H₂O)]²⁺, 2 are linked by non-covalent interactions. This compound, along with the one previously synthesized by us, [Ru^II(trpy)(bpy)(H₂O)][(3,3'-Co(1,2-C₂B₉H₁₁)₂]₂, 4, are the only examples of cooperative molecular photocatalysts in which the catalyst and photosensitizer are not linked by covalent bonds. Both cooperative systems have proven to be efficient photocatalysts for the oxidation of alkenes in water through Proton Coupled Electron Transfer processes (PCETs). Using 0.05 mol% of catalyst 4, total conversion values were achieved after 15 min with moderate selectivity for the corresponding epoxides, which decreases with reaction time, along with the TON values. However, with 0.005 mol% of catalyst, the conversion values are lower, but the selectivity and TON values are higher. This occurs simultaneously with an increase in the amount of the corresponding diol for most of the substrates studied. Photocatalyst 4 acts as a photocatalyst in both the epoxidation of alkenes and their hydroxylation in aqueous medium. The hybrid system 5 shows generally higher conversion values at low loads compared to those obtained with 4 for most of the substrates studied. However, the selectivity values for the corresponding epoxides are lower even after 15 min of reaction. This is likely due to the enhanced oxidizing capacity of Co^IV in catalyst 5, resulting from the presence of more electron-withdrawing substituents on the metallacarborane platform.