Mechanistic Study on the Photogeneration of Hydrogen by Decamethylruthenocene

Abstract

Detailed studies on hydrogen evolution by decamethylruthenocene ([Cp*₂ Ru^II ]) highlighted that metallocenes are capable of photoreducing hydrogen without the need for an additional sensitizer. Electrochemical, gas chromatographic, and spectroscopic (UV/Vis, ¹ H and ¹³ C NMR) measurements corroborated by DFT calculations indicated that the production of hydrogen occurs by a two-step process. First, decamethylruthenocene hydride [Cp*₂ Ru^IV (H)]⁺ is formed in the presence of an organic acid. Subsequently, [Cp*₂ Ru^IV (H)]⁺ is reversibly reduced in a heterolytic reaction with one-photon excitation leading to a first release of hydrogen. Thereafter, the resultant decamethylruthenocenium ion [Cp*₂ Ru^III ]⁺ is further reduced with a second release of hydrogen by deprotonation of a methyl group of [Cp*₂ Ru^III ]⁺ . Experimental and computational data show spontaneous conversion of [Cp*₂ Ru^II ] to [Cp*₂ Ru^IV (H)]⁺ in the presence of protons. Calculations highlight that the first reduction is endergonic (ΔG⁰ =108 kJ mol^-1 ) and needs an input of energy by light for the reaction to occur. The hydricity of the methyl protons of [Cp*₂ Ru^II ] was also considered.