Electrochemical Generation and Spectroscopic Characterization of the Key Rhodium(III) Hydride Intermediates of Rhodium Poly(bipyridyl) H 2 -Evolving Catalysts

We previously reported that the [Rh (dmbpy) Cl ] (dmbpy = 4,4'-dimethyl-2,2'-bipyridine) complex is an efficient H -evolving catalyst in water when used in a molecular homogeneous photocatalytic system for hydrogen production with [Ru (bpy) ] (bpy = 2,2'-bipyridine) as photosensitizer...

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Published in:Inorganic chemistry 2018-09, Vol.57 (17), p.11225-11239
Main Authors: Castillo, Carmen E, Stoll, Thibaut, Sandroni, Martina, Gueret, Robin, Fortage, Jérôme, Kayanuma, Megumi, Daniel, Chantal, Odobel, Fabrice, Deronzier, Alain, Collomb, Marie-Noëlle
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Language:English
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Chemical Sciences
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Summary:We previously reported that the [Rh (dmbpy) Cl ] (dmbpy = 4,4'-dimethyl-2,2'-bipyridine) complex is an efficient H -evolving catalyst in water when used in a molecular homogeneous photocatalytic system for hydrogen production with [Ru (bpy) ] (bpy = 2,2'-bipyridine) as photosensitizer and ascorbic acid as sacrificial electron donor. The catalysis is believed to proceed via a two-electron reduction of the Rh(III) catalyst into the square-planar [Rh (dmbpy) ] , which reacts with protons to form a Rh(III) hydride intermediate that can, in turn, release H following different pathways. To improve the current knowledge of these key intermediate species for H production, we performed herein a detailed electrochemical investigation of the [Rh (dmbpy) Cl ] and [Rh (dtBubpy) Cl ] (dtBubpy = 4,4'-di- tert-butyl-2,2'-bipyridine) complexes in CH CN, which is a more appropriate medium than water to obtain reliable electrochemical data. The low-valent [Rh (Rbpy) ] and, more importantly, the hydride [Rh (Rbpy) (H)Cl] species (R = dm or dtBu) were successfully electrogenerated by bulk electrolysis and unambiguously spectroscopically characterized. The quantitative formation of the hydrides was achieved in the presence of weak proton sources (HCOOH or CF CO H), owing to the fast reaction of the electrogenerated [Rh (Rbpy) ] species with protons. Interestingly, the hydrides are more difficult to reduce than the initial Rh(III) bis-chloro complexes by ∼310-340 mV. Besides, 0.5 equiv of H is generated through their electrochemical reduction, showing that Rh(III) hydrides are the initial catalytic molecular species for hydrogen evolution. Density functional theory calculations were also performed for the dmbpy derivative. The optimized structures and the theoretical absorption spectra were calculated for the initial bis-chloro complex and for the various rhodium intermediates involved in the H evolution process.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.8b01811