Electrochemical ruthenium-catalysed C–H activation in water through heterogenization of a molecular catalyst

Abstract

Efficient catalytic oxidative C–H activation of organic substrates remains an important challenge in synthetic chemistry. Here, we show that the combination of a transition metal catalyst, surface immobilisation and an electrochemical potential provide a promising approach to effecting these transformations in aqueous solution. A ruthenium-based molecular catalyst [Ru(tpy)(pic-PO3H2)(Cl)] (where tpy is 2,2′:6′,2′′-terpyridine, pic-PO3H2 is 4-phosphonopyrid-2-ylcarboxylic acid) was synthesised and fully characterised. Oxidation of benzyl alcohol with the catalyst in aqueous media using ceric ammonium nitrate as terminal oxidant resulted in a rapid deactivation of the catalyst. Immobilisation of the catalyst on a mesoporous indium tin oxide electrode surface through the phosphonate anchoring group was shown to circumvent the issues observed in solution. Using the heterogeneous catalyst system, the oxidation of a variety of organic substrates with varying bond dissociation energies was demonstrated with turnover numbers of up to 346. Finally, surface-analysis of the functionalised electrodes after catalysis revealed that fragmentation of the complex during the reaction was the limiting factor for catalytic performance.