Ru(ii) water oxidation catalysts with 2,3-bis(2-pyridyl)pyrazine and tris(pyrazolyl)methane ligands: assembly of photo-active and catalytically active subunits in a dinuclear structure

Abstract

Two mononuclear Ru(II) complexes, i.e. [RuCl(κ³N-terpy)(κ²N-dpp)]PF₆ ([1]PF₆; terpy = 2,2′:6′,2′′-terpyridine; dpp = 2,3-bis(2′-pyridyl-pyrazine) and [RuCl(κ³N-tpm)(κ²N-dpp)]Cl ([2]Cl; tpm = tris(1-pyrazolyl)methane), and one dinuclear complex, i.e. [Ru₂Cl(κ³N-tpm)(μ-κ²N:κ²N-dpp)Ru(κ²N-bpy)₂][PF₆]₃ ([3][PF₆]₃; bpy = 2,2′-bipyridine), have been synthesized and their water oxidation catalytic properties have been investigated. A combined DFT and experimental (³⁵Cl NMR and conductivity measurements) study aimed to elucidate the nature of [1]⁺ and [2]⁺ in aqueous solution has also been performed, indicating that one water molecule is allowed to enter the first coordination sphere of [2]⁺ in the ground state, replacing one tpm nitrogen. Conversely, in the case of [1]⁺, water coordination, assumed to be needed for the water oxidation process, presumably occurs following the oxidation of the metal. For all complexes, a catalytic wave has been detected in acetonitrile/water 1 : 1 (v/v) solution in the range 1.4–1.7 V vs. SCE. In all cases, water oxidation (investigated at pH < 8) takes place initially via a proton-coupled two-electron, two-proton process with the formation of an Ru(IV)O moiety, followed by one electron oxidation and water nucleophilic attack. The TON and TOF values (within the range of 16–33 and 1.3–2.2 h⁻¹, respectively) of the complexes are higher than those of the benchmark [Ru(LLL)(LL)(OH₂)]²⁺-type species (LLL and LL are tridentate and bidentate polypyridine ligands, respectively), which is [Ru(terpy)(bpm)(OH₂)]²⁺.