Metal-ligand cooperativity in chemical electrosynthesis.

Electrochemistry has been an increasingly useful tool for organic synthesis, as it can selectively generate reactive intermediates under mild conditions using an applied potential. Concurrently, synergistic activity of a metal and a ligand has been used in thermal catalysis and electrocatalytic renewable fuel generation for substrate selectivity and improved catalyst activity. Combining these synthetic strategies is an attractive approach for mild, selective, and sustainable electrosynthesis. This perspective discusses examples of metal-ligand synergistic catalysis in electrochemical applications in organic and organometallic synthesis. The range of reactions and ligand design principles illustrates many opportunities for further discovery in this area and the potential for far-reaching synthetic benefits.

Catalytic, Spectroscopic, and Theoretical Studies of Fe4S4-Based Coordination Polymers as Heterogenous Coupled Proton-Electron Transfer Mediators for Electrocatalysis.

Iron-sulfur clusters play essential roles in biological systems, and thus synthetic [Fe4S4] clusters have been an area of active research. Recent studies have demonstrated that soluble [Fe4S4] clusters can serve as net H atom transfer mediators, improving the activity and selectivity of a homogeneous Mn CO2 reduction catalyst. Here, we demonstrate that incorporating these [Fe4S4] clusters into a coordination polymer enables heterogeneous H atom transfer from an electrode surface to a Mn complex dissolved in solution. A previously reported solution-processable Fe4S4-based coordination polymer was successfully deposited on the surfaces of different electrodes. The coated electrodes serve as H atom transfer mediators to a soluble Mn CO2 reduction catalyst displaying good product selectivity for formic acid. Furthermore, these electrodes are recyclable with a minimal decrease in activity after multiple catalytic cycles. The heterogenization of the mediator also enables the characterization of solution-phase and electrode surface species separately. Surface enhanced infrared absorption spectroscopy (SEIRAS) reveals spectroscopic signatures for an in situ generated active Mn-H species, providing a more complete mechanistic picture for this system. The active species, reaction mechanism, and the protonation sites on the [Fe4S4] clusters were further confirmed by density functional theory calculations. The observed H atom transfer reactivity of these coordination polymer-coated electrodes motivates additional applications of this composite material in reductive H atom transfer electrocatalysis.

Electrocatalytic Semihydrogenation of Terminal Alkynes Using Ligand-Based Transfer of Protons and Electrons.

Alkyne semihydrogenation is a broadly important transformation in chemical synthesis. Here, we introduce an electrochemical method for the selective semihydrogenation of terminal alkynes using a dihydrazonopyrrole Ni complex capable of storing an H2 equivalent (2H+ + 2e-) on the ligand backbone. This method is chemoselective for the semihydrogenation of terminal alkynes over internal alkynes or alkenes. Mechanistic studies reveal that the transformation is concerted and Z-selective. Calculations support a ligand-based hydrogen-atom transfer pathway instead of a hydride mechanism, which is commonly invoked for transition metal hydrogenation catalysts. The synthesis of the proposed intermediates demonstrates that the catalytic mechanism proceeds through a reduced formal Ni(I) species. The high yields for terminal alkene products without over-reduction or oligomerization are among the best reported for any homogeneous catalyst. Furthermore, the metal-ligand cooperative hydrogen transfer enabled with this system directs the efficient flow of H atom equivalents toward alkyne reduction rather than hydrogen evolution, providing a blueprint for applying similar strategies toward a wide range of electroreductive transformations.

Electrocatalytic C-H activation and fluorination using high-valent Cu.

In this issue of Chem Catalysis, Zhang and co-workers demonstrate the utility of electrochemical methods to enable catalytic turnover, employing high-valent Cu for C-H bond fluorination with selectivity for more hydridic bonds. Corresponding mechanistic investigations offer a rare catalytic example of oxidation driven C-H activation.

Dynamic properties of a self-replicating peptide network with inhibition.

In this paper, we report an open system consisting of three self-replicating peptides, in which peptide 1 inhibits the duplex template of peptide 2, peptide 2 inhibits duplex 3, and peptide 3 inhibits duplex 1 to complete the negative feedback loop. This interacting chemical network yields oscillations in the concentrations of all species over time and establishes a possible mechanism for pre-biotic chemical systems organization. The first focus of our analysis is the effect of altering rates of duplex formation and inhibition on oscillations. We then examine the autocatalytic rate constant in the symmetric and asymmetric cases.

Generation and Aerobic Oxidative Catalysis of a Cu(II) Superoxo Complex Supported by a Redox-Active Ligand.

Cu systems feature prominently in aerobic oxidative catalysis in both biology and synthetic chemistry. Metal ligand cooperativity is a common theme in both areas as exemplified by galactose oxidase and by aminoxyl radicals in alcohol oxidations. This has motivated investigations into the aerobic chemistry of Cu and specifically the isolation and study of Cu-superoxo species that are invoked as key catalytic intermediates. While several examples of complexes that model biologically relevant Cu(II) superoxo intermediates have been reported, they are not typically competent aerobic catalysts. Here, we report a new Cu complex of the redox-active ligand tBu,TolDHP (2,5-bis((2-t-butylhydrazono)(p-tolyl)methyl)-pyrrole) that activates O2 to generate a catalytically active Cu(II)-superoxo complex via ligand-based electron transfer. Characterization using ultraviolet (UV)-visible spectroscopy, Raman isotope labeling studies, and Cu extended X-ray absorption fine structure (EXAFS) analysis confirms the assignment of an end-on κ1 superoxo complex. This Cu-O2 complex engages in a range of aerobic catalytic oxidations with substrates including alcohols and aldehydes. These results demonstrate that bioinspired Cu systems can not only model important bioinorganic intermediates but can also mediate and provide mechanistic insight into aerobic oxidative transformations.

Direct Aerobic Generation of a Ferric Hydroperoxo Intermediate Via a Preorganized Secondary Coordination Sphere.

Enzymes exert control over the reactivity of metal centers with precise tuning of the secondary coordination sphere of active sites. One particularly elegant illustration of this principle is in the controlled delivery of proton and electron equivalents in order to activate abundant but kinetically inert oxidants such as O2 for oxidative chemistry. Chemists have drawn inspiration from biology in designing molecular systems where the secondary coordination sphere can shuttle protons or electrons to substrates. However, a biomimetic activation of O2 requires the transfer of both protons and electrons, and molecular systems where ancillary ligands are designed to provide both of these equivalents are comparatively rare. Here, we report the use of a dihydrazonopyrrole (DHP) ligand complexed to Fe to perform exactly such a biomimetic activation of O2. In the presence of O2, this complex directly generates a high spin Fe(III)-hydroperoxo intermediate which features a DHP• ligand radical via ligand-based transfer of an H atom. This system displays oxidative reactivity and ultimately releases hydrogen peroxide, providing insight on how secondary coordination sphere interactions influence the evolution of oxidizing intermediates in Fe-mediated aerobic oxidations.

Metal-Ligand Cooperative Transfer of Protons and Electrons.

Realizing cooperativity between ligands and metal centers in the transfer of proton and electron equivalents has the potential to facilitate faster, selective, and novel transformations. Recent advances in the synthesis and application of ligands with these design features illustrate the value of this biomimetic strategy in synthetic chemistry.