An original cooperative photoredox catalytic system, [Ru-II(trpy)(bpy)(H2O)][3,3'-Co(1,2-C2B9H11)(2)](2) (C4; trpy = terpyridine and bpy = bipyridine), has been synthesized. In this system, the photoredox metallacarborane catalyst [3,3'-Co(1,2-C2B9H11)(2)](-) ([1](-)) and the oxidation catalyst [Ru-II(trpy)(bpy)(H2O)](2+) (C2') are linked by noncovalent interactions and not through covalent bonds. The noncovalent interactions to a large degree persist even after water dissolution. This represents a step ahead in cooperativity avoiding costly covalent bonding. Recrystallization of C4 in acetonitrile leads to the substitution of water by the acetonitrile ligand and the formation of complex [Ru-II(trpy)(bpy)(CH3CN)][3,3'-Co(1,2-C2B9H11)(2)](2) (C5), structurally characterized. A significant electronic coupling between C2' and [1](-) was first sensed in electrochemical studies in water. The Co-IV/III redox couple in water differed by 170 mV when [1](-) had Na+ as a cation versus when the ruthenium complex was the cation. This cooperative system leads to an efficient catalyst for the photooxidation of alcohols in water, through a proton-coupled electron-transfer process. We have highlighted the capacity of C4 to perform as an excellent cooperative photoredox catalyst in the photooxidation of alcohols in water at room temperature under UV irradiation, using 0.005 mol % catalyst. A high turnover number (TON = 20000) has been observed. The hybrid system C4 displays a better catalytic performance than the separated mixtures of C2' and Na[1], with the same concentrations and ratios of Ru/Co, proving the history relevance of the photocatalyst. Cooperative systems with this type of interaction have not been described and represent a step forward in getting cooperativity avoiding costly covalent bonding. A possible mechanism has been proposed.
