The development of safe and energy efficient redox processes is key for a future sustainable organic chemistry and energy storage/vector applications. Molecular electrocatalysts have demonstrated their potential in the realm of CO 2 reduction, however, successful implementations for the reduction of other carbonyl groups remain sporadic. Building on the reversibility of hydrogenation and dehydrogenation of carbonyls and alcohols, an overview of current molecular electrocatalytic systems is presented. Key mechanistic concepts are emphasized to facilitate the link with more mature schemes in transfer hydrogenation, proton-and CO 2 -reduction. Thus, this work contributes to future catalyst generation development bridging fundamental aspects of electrochemical bond activation with molecular catalytic concepts in the context of societal challenges of today.
Diphosphine ligands are frequently used in palladium-catalyzed Suzuki-Miyaura (S-M) reactions. Despite their widespread application in both academic and industrial settings, their role in the B-to-Pd transmetalation has not been firmly established. We combined electrochemistry, NMR spectroscopy and DFT calculations to elucidate the role of dppf (1,1'-bis(diphenylphosphino)ferrocene) in this key elementary step of the S-M reaction. We observed that excess dppf inhibits transmetalation involving PhB(OH)2 and dppf-ligated arylpalladium(II) complexes, while an optimal [base]/[PhB(OH)2] ratio maximizes the concentration of a [Pd-O-B] key intermediate. In situ oxidation of dppf to the diphosphine monoxide dppfO can take place in the presence of base, leading to dppfO-ligated arylpalladium(II) complexes, which readily undergo transmetalation at room temperature. These findings suggest guidelines for the rational optimization of diphosphine-promoted S-M reactions.
Novel energy and atom efficiency processes will be keys to develop the sustainable chemical industry of the future. Electrification could play an important role, by allowing to fine-tune energy input...
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