Enhanced hydrogen generation from formic acid by a biomimetic ruthenium complex with a covalently bonded phosphine ligand

Embedding a Ruthenium-Based Structural Mimic of the [Fe]-Hydrogenase Cofactor into Papain

“…16 Ruthenium complexes are generally more air-stable than their iron counterparts, and many are known to activate dihydrogen. 17,18 We therefore hypothesized that a reproduction of the [Fe]-hydrogenase using a more stable ruthenium model complex and an appropriate protein scaffold may serve as a useful model for studying aspects of its chemistry. Such metalloenzymes are also of interest as possibly possessing unique catalytic properties.…”

High-Rate Hydrogen Generation by Direct Sunlight Irradiation with a Triruthenium Complex

“…In the quest for high-rate H 2 generation, researchers have investigated a multitude of organic, inorganic, biohybrid, or bioinspired catalysts to catalyze water splitting or biomass conversion to H 2 . − Maintaining a sustainable supply of H 2 from aqueous media, with the exception of electrolysis of water, remains a challenge because of low turnover numbers and frequencies. To date, significant progress has been achieved in developing better catalysts for the release of H 2 from biomass originating from methanol, ethanol, and formic acid (FA), which can be easily handled, stored, and transported in their liquid forms under ambient conditions. − …”

“…Recently, a diruthenium-based biomimetic H-cluster system, based on the H-cluster of the [FeFe]-H 2 ases, was reported and applied to a photocatalytic H 2 production study in the presence of covalently and noncovalently linked phosphine ligands and FA . A high catalytic activity, represented by a TOF of 15840 h –1 , was obtained with less than 50 ppm of the catalyst present .…”

A comparative study of the electrochemical and proton-reduction behaviour of diphosphine-dithiolate complexes [M2(CO)4(μ-dppm){μ-S(CH2) n S}] (M = Fe, Ru; n = 2, 3)

“…Consequently a large number of diphosphine-bridged diiron-dithiolate complexes have been reported [23][24][25][26][27][28][29][30][31][32] but surprisingly little attention has been paid to their proton-reduction chemistry [27-32] even though some, for example [Fe 2 (CO) 4 (l-dppf)(l-pdt)] (dppf = 1,1 0 -bis(diphenylphosphino)ferrocene), have been shown to be efficient proton-reduction catalysts [29]. Similarly, given the large number of diiron complexes tested as proton-reduction catalysts, related diruthenium complexes have not been widely studied [53][54][55][56]. Herein we detail a comparative investigation of the electrochemistry and proton-reduction behaviour of diiron and diruthenium complexes [M 2 (CO) 4 (ldppm)(l-pdt)] [24,27,57] and [M 2 (CO) 4 (l-dppm)(l-edt)] [26,27,57] (Fig.…”