Diruthenium Catalyst for Hydrogen Production from Aqueous Formic Acid.

Diruthenium complexes [{(η6-arene)RuCl}2(µ-κ2:κ2-benztetraimd)]2+ containing the bridging bis-imidazole methane-based ligand {1,4-bis(bis(2-ethyl-5-methyl-1H-imidazol-4-yl)methyl)benzene} (benztetraimd) are synthesized for catalytic formic acid dehydrogenation in water at 90 °C. Catalyst [{(η6-p-cymene)RuCl}2(µ-κ2:κ2-benztetraimd)]2+ [1-Cl2] exhibited a remarkably high turnover frequency (1993 h-1 per Ru atom) and long-term stability over 60 days for formic acid dehydrogenation, while the analogous (η6-benzene)diruthenium and mononuclear catalysts displayed low activity with poor long-term stability. Notably, catalyst [1-Cl2] also displayed an appreciably high turnover number of 93 200 for the bulk-scale reaction. In addition, the in-depth mass and nuclear magnetic resonance investigations under the catalytic and control experimental conditions revealed the active involvement of several crucial catalytic intermediate species, such as Ru-aqua species [{(η6-p-cymene)Ru(H2O)}2(µ-L)]2+ [1-(OH2)2], Ru-formato species [{(η6-p-cymene)Ru(HCOO)}2(µ-L)] [1-(HCOO)2], and Ru-hydrido species [{(η6-p-cymene)Ru(H)}2(µ-L)] [1-(H)2], in the catalytic formic acid dehydrogenation reaction.

Proton reduction by a bimetallic zinc selenolate electrocatalyst.

The development of alternative energy sources is the utmost priority of developing society. Unlike many prior homogeneous electrocatalysts that rely on a change in the oxidation state of the metal center and/or electrochemically active ligand, here we report the synthesis and structural characterization of a bimetallic zinc selenolate complex consisting of a redox silent zinc metal ion and a tridentate ligand that catalyzes the reduction of protons into hydrogen gas electrochemically and displays one of the highest reported TOF for a homogeneous TM-metal free ligand centered HER catalyst, 509 s-1. The current-voltage analysis confirms the onset overpotential of 0.86 V vs. Ag/AgCl for the HER process. Constant potential electrolysis (CPE) has been carried out to study the bulk electrolysis of our developed protocol, which reveals that the bimetallic zinc selenolate catalyst is stable under cathodic as well as anodic potentials and generates hydrogen gas with a faradaic efficiency of 75%. Preliminary studies on the heterogeneous catalyst were conducted by depositing the bimetallic zinc selenolate catalyst on the electrode surface.

Synthesis, structure and catalytic activity of manganese(ii) complexes derived from bis(imidazole)methane-based ligands.

New mononuclear manganese(ii) complexes [Mn(κ2-L1)(OAc)2] ([Mn]-1), [Mn(κ2-L2)(OAc)2] ([Mn]-2) and [Mn(κ2-L3)(OAc)2] ([Mn]-3) with imidazole based ligands {4,4'-(phenylmethylene)bis(2-ethyl-5-methyl-1H-imidazole)} (L1), {(4,4'-((2-methoxy phenyl)methylene)bis(2-ethyl-5-methyl-1H-imidazole)} (L2) and {4,4'-((2-chlorophenyl) methylene)bis(2-ethyl-5-methyl-1H-imidazole)} (L3) are synthesized and fully characterized by a variety of techniques. Furthermore, the molecular structures of complexes [Mn]-1 and [Mn]-2 are established by single crystal X-ray structure analysis. The synthesized manganese(ii) complexes exhibited efficient catalytic oxidative coupling of primary amines in air under solvent-free conditions to the corresponding imines in moderate to good yields.

Ruthenium Complexes for Catalytic Dehydrogenation of Hydrazine and Transfer Hydrogenation Reactions.

Catalytic dehydrogenation of hydrazine was achieved over iminopyridine ligated ruthenium-arene complexes, where the release of H2 gas, as confirmed by GC-TCD, from hydrazine depends on reaction temperature, base, and solvents. NMR and MS studies indicated an in situ generation of a hydrazine-coordinated ruthenium species, a key intermediate of hydrazine dehydrogenation, via a coordination-assisted activation pathway.