Coupling between two Ru(bda) catalysts bridged by a trans -dicyano complex

Abstract

We have prepared two trimetallic complexes [{Ru(bda)(DMSO)(μ-CN)}2Ru(L)4] (with bda = 2,2′-bipyridine-6,6′-dicarboxylate) where two {Ru(bda)} centers are bridged by a cyanide complex of the trans-Ru(L)4CN2 family (with L = pyridine and 4-tert-butylpyridine). The complex [{Ru(bda)(DMSO)(μ-CN)}2Ru(py)4] is fully soluble in aqueous solution and is a catalyst for the oxidation of water both chemically, using Ce(IV) at pH = 1 as the terminal oxidant, and electrochemically. Both reactions are first order in the complex and the resting state of the catalyst is the [RuVRuIII(py)4RuIV]2+ redox state. Electrochemical and spectroelectrochemical studies together with (TD)DFT calculations show that the coupling between the Ru(bda) fragments for the [RuIIIRuII(py)4RuIII]2+ and [RuIVRuII(py)4RuIV]2+ redox states is very weak, but significant for the [RuVRuII(py)4RuIV]2+ ion due to the orientation of the orbitals involved. This coupling affects the reactivity of the [RuVRuII(py)4RuIV]2+ redox state, making it a much slower catalyst towards the water oxidation reaction than [RuVRuIII(py)4RuIV]2+.