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Reduction of β-diketiminato nickel(II) complexes (LtBuNiII) to the corresponding nickel(I) compounds does not require alkali metal compounds but can also be performed with the milder cobaltocenes. LtBuNiBr and Cp2Co have rather similar redox potentials, so that the equilibrium with the corresponding electron transfer compound [LtBuNiIBr][Cp2CoIII] (ETC) clearly lies on the side of the starting materials. Still, the ETC portion can be used to activate CO2 yielding a mononuclear nickel(II) carbonate complex and ETC can be isolated almost quantitatively from the solutions through crystallisation. The more negative reduction potential of Cp*2Co shifts the equilibrium formed with LtBuNiBr strongly towards the ETC and accordingly the reaction of such solutions with CO2 is much faster. [ABSTRACT FROM AUTHOR]

Reduction of β-diketiminato nickel(II) complexes (LtBuNiII) to the corresponding nickel(I) compounds does not require alkali metal compounds but can also be performed with the milder cobaltocenes. LtBuNiBr and Cp2Co have rather similar redox potentials, so that the equilibrium with the corresponding electron transfer compound [LtBuNiIBr][Cp2CoIII] (ETC) clearly lies on the side of the starting materials. Still, the ETC portion can be used to activate CO2 yielding a mononuclear nickel(II) carbonate complex and ETC can be isolated almost quantitatively from the solutions through crystallisation. The more negative reduction potential of Cp*2Co shifts the equilibrium formed with LtBuNiBr strongly towards the ETC and accordingly the reaction of such solutions with CO2 is much faster. [ABSTRACT FROM AUTHOR]

We have prepared several 2,5,8-trialkoxyheptazines starting from the soluble precursor 2,5,8-tris(3,5-diethylpyrazolyl)-heptazine. We present their synthesis along with their promising spectroscopic and electrochemical properties, which demonstrate large band gaps and high reduction potentials altogether. Subsequently, we provide a short assessment of the promising ability of one of these molecules to perform catalytic oxidation test-reactions. [ABSTRACT FROM AUTHOR]

A highly reducing diquat-type molecule was explored as a negative electrolyte for nonaqueous redox flow batteries. The molecule displays a highly negative 2+/0 reduction potential of −1.67 V (vs. ferrocene), a low mass per electron transferred, and good solubility in CH3CN in both redox states. Moderate capacity retention is observed during electrochemical charge–discharge cycling. A pathway for decomposition during electrochemical cycling is elucidated, and this provides a clear path forward for enhancing stability. [ABSTRACT FROM AUTHOR]

Herein, we report a new donor–acceptor system for photo-induced proton-coupled electron transfer (PCET) that leverages an azo linkage as the proton-sensitive component and anthracene as a photo-trigger. Electrochemistry shows a change in the reduction potential with addition of acid. However, photochemistry is invariant to the absence or presence of acid. The anthracene and phenol/4-methoxyphenyl moieties of the azo dyes are highly conjugated, likely mitigating photo-induced charge transfer, despite sufficient driving force. [ABSTRACT FROM AUTHOR]

A series of viologen related redox mediators of varying reduction potential has been characterized and their utility as electron shuttles between CdSe quantum dots and hydrogenase enzyme has been demonstrated. Tuning the mediator LUMO energy optimizes the performance of this hybrid photocatalytic system by balancing electron transfer rates of the shuttle. [ABSTRACT FROM AUTHOR]

Two new nickel dithiolate derivatives have been examined for their electrocatalytic activity for the hydrogen evolution reaction (HER) in attempts to clarify whether the overpotential for the HER can be tuned upon varying the ligand-centered reduction potential that triggers the HER by the catalysts. We demonstrate the validity of this approach to achieve desirable tunability in the overpotential for the HER. [ABSTRACT FROM AUTHOR]