Electrochemical Properties of a Rhodium(III) Mono-Terpyridyl Complex and Use as a Catalyst for Light-Driven Hydrogen Evolution in Water

Molecular hydrogen (H(2)) is considered one of the most promising fuels to decarbonize the industrial and transportation sectors, and its photocatalytic production from molecular catalysts is a research field that is still abounding. The search for new molecular catalysts for H(2) production with simple and easily synthesized ligands is still ongoing, and the terpyridine ligand with its particular electronic and coordination properties, is a good candidate to design new catalysts meeting these requirements. Herein, we have isolated the new mono-terpyridyl rhodium complex, [Rh(III)(tpy)(CH(3)CN)Cl(2)](CF(3)SO(3)) (Rh-tpy), and shown that it can act as a catalyst for the light-induced proton reduction into H(2) in water in the presence of the [Ru(bpy)(3)]Cl(2) (Ru) photosensitizer and ascorbate as sacrificial electron donor. Under photocatalytic conditions, in acetate buffer at pH 4.5 with 0.1 M of ascorbate and 530 μM of Ru, the Rh-tpy catalyst produces H(2) with turnover number versus catalyst (TON(Cat)*) of 300 at a Rh concentration of 10 μM, and up to 1000 at a concentration of 1 μM. The photocatalytic performance of Ru/Rh-tpy/HA(–)/H(2)A has been also compared with that obtained with the bis-dimethyl-bipyridyl complex [Rh(III)(dmbpy)(2)Cl(2)](+) (Rh2) as a catalyst in the same experimental conditions. The investigation of the electrochemical properties of Rh-tpy in DMF solvent reveals that the two-electrons reduced state of the complex, the square-planar [Rh(I)(tpy)Cl] (Rh(I)-tpy), is quantitatively electrogenerated by bulk electrolysis. This complex is stable for hours under an inert atmosphere owing to the π-acceptor property of the terpyridine ligand that stabilizes the low oxidation states of the rhodium, making this catalyst less prone to degrade during photocatalysis. The π-acceptor property of terpyridine also confers to the Rh-tpy catalyst a moderately negative reduction potential (Ep(c)(Rh(III)/Rh(I)) = −0.83 V vs. SCE in DMF), making possible its reduction by the reduced state of Ru, [Ru(II)(bpy)(bpy(•−))](+) (Ru(−)) (E(1/2)(Ru(II)/Ru(−)) = −1.50 V vs. SCE) generated by a reductive quenching of the Ru excited state (*Ru) by ascorbate during photocatalysis. A Stern–Volmer plot and transient absorption spectroscopy confirmed that the first step of the photocatalytic process is the reductive quenching of *Ru by ascorbate. The resulting reduced Ru species (Ru(−)) were then able to activate the Rh(III)-tpy H(2)-evolving catalyst by reduction generating Rh(I)-tpy, which can react with a proton on a sub-nanosecond time scale to form a Rh(III)(H)-tpy hydride, the key intermediate for H(2) evolution.