Photodriven Sm(III)-to-Sm(II) Reduction for Catalytic Applications.

The selectivity of SmI2 as a one electron-reductant motivates the development of methods for reductive Sm-catalysis. Photochemical methods for SmI2 regeneration are desired for catalytic transformations. In particular, returning SmIII-alkoxides to SmII is a crucial step for Sm-turnover in many potential applications. To this end, photochemical conditions for reduction of both SmI3 and a model SmIII-alkoxide to SmI2(THF)n are described here. The Hantzsch ester can serve either as a direct photoreductant or as the reductive quencher for an Ir-based photoredox catalyst. In contrast to previous SmIII reduction methodologies, no Lewis acidic additives or byproducts are involved, facilitating selective ligand coordination to Sm. Accordingly, SmII species can be generated photochemically from SmI3 in the presence of protic, chiral, and/or Lewis basic additives. Both the photoreductant and photoredox methods for SmI2 generation translate to intermolecular ketone-acrylate coupling as a proof-of-concept demonstration of a photodriven, Sm-catalyzed reductive cross-coupling reaction.

Electrochemical CO2 Reduction in Acidic Electrolytes: Spectroscopic Evidence for Local pH Gradients.

Inspired by recent advances in electrochemical CO2 reduction (CO2R) under acidic conditions, herein we leverage in situ spectroscopy to inform the optimization of CO2R at low pH. Using attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and fluorescent confocal laser scanning microscopy, we investigate the role that alkali cations (M+) play on electrochemical CO2R. This study hence provides important information related to the local electrode surface pH under bulk acidic conditions for CO2R, both in the presence and absence of an organic film layer, at variable [M+]. We show that in an acidic electrolyte, an appropriate current density can enable CO2R in the absence of metal cations. In situ local pH measurements suggest the local [H+] must be sufficiently depleted to promote H2O reduction as the competing reaction with CO2R. Incrementally incorporating [K+] leads to increases in the local pH that promotes CO2R but only at proton consumption rates sufficient to drive the pH up dramatically. Stark tuning measurements and analysis of surface water structure reveal no change in the electric field with [M+] and a desorption of interfacial water, indicating that improved CO2R performance is driven by suppression of H+ mass transport and modification of the interfacial solvation structure. In situ pH measurements confirm increasing local pH, and therefore decreased local [CO2], with [M+], motivating alternate means of modulating proton transport. We show that an organic film formed via in situ electrodeposition of an organic additive provides a means to achieve selective CO2R (FECO2R ∼ 65%) over hydrogen evolution reaction in the presence of strong acid (pH 1) and low cation concentrations (≤0.1 M) at both low and high current densities.

Reductive samarium (electro)catalysis enabled by SmIII-alkoxide protonolysis.

Samarium diiodide (SmI2) is a privileged, single-electron reductant deployed in diverse synthetic settings. However, generalizable methods for catalytic turnover remain elusive because of the well-known challenge associated with cleaving strong SmIII-O bonds. Prior efforts have focused on the use of highly reactive oxophiles to enable catalyst turnover. However, such approaches give rise to complex catalyst speciation and intrinsically limit the synthetic scope. Herein, we leveraged a mild and selective protonolysis strategy to achieve samarium-catalyzed, intermolecular reductive cross-coupling of ketones and acrylates with broad scope. The modularity of our approach allows rational control of selectivity based on solvent, pKa (where Ka is the acid dissociation constant), and the samarium coordination sphere and provides a basis for future developments in catalytic and electrocatalytic lanthanide chemistry.

Intermolecular Proton-Coupled Electron Transfer Reactivity from a Persistent Charge-Transfer State for Reductive Photoelectrocatalysis.

Interest in applying proton-coupled electron transfer (PCET) reagents in reductive electro- and photocatalysis requires strategies that mitigate the competing hydrogen evolution reaction. Photoexcitation of a PCET donor to a charge-separated state (CSS) can produce a powerful H-atom donor capable of being electrochemically recycled at a comparatively anodic potential corresponding to its ground state. However, the challenge is designing a mediator with a sufficiently long-lived excited state for bimolecular reactivity. Here, we describe a powerful ferrocene-derived photoelectrochemical PCET mediator exhibiting an unusually long-lived CSS (τ ∼ 0.9 µs). In addition to detailed photophysical studies, proof-of-concept stoichiometric and catalytic proton-coupled reductive transformations are presented, which illustrate the promise of this approach.

Electrode Surface Heating with Organic Films Improves CO2 Reduction Kinetics on Copper.

Management of the electrode surface temperature is an understudied aspect of (photo)electrode reactor design for complex reactions, such as CO2 reduction. In this work, we study the impact of local electrode heating on electrochemical reduction of CO2 reduction. Using the ferri/ferrocyanide open circuit voltage as a reporter of the effective reaction temperature, we reveal how the interplay of surface heating and convective cooling presents an opportunity for cooptimizing mass transport and thermal assistance of electrochemical reactions, where we focus on reduction of CO2 to carbon-coupled (C2+) products. The introduction of an organic coating on the electrode surface facilitates well-behaved electrode kinetics with near-ambient bulk electrolyte temperature. This approach helps to probe the fundamentals of thermal effects in electrochemical reactions, as demonstrated through Bayesian inference of Tafel kinetic parameters from a suite of high throughput experiments, which reveal a decrease in overpotential for C2+ products by 0.1 V on polycrystalline copper via 60 °C surface heating.

Catalytic Reduction of Cyanide to Ammonia and Methane at a Mononuclear Fe Site.

Nitrogenase enzymes catalyze nitrogen reduction (N2R) to ammonia and also the reduction of non-native substrates, including the 7H+/6e- reduction of cyanide to CH4 and NH3. CN- and N2 are isoelectronic, and it is hence fascinating to compare the mechanisms of synthetic Fe catalysts capable of both CN- and N2 reduction. Here, we describe the catalytic reduction of CN- to NH3 and CH4 by a highly selective (P3Si)Fe(CN) catalyst (P3Si represents a tris(phosphine)silyl ligand). Catalysis is driven in the presence of excess acid ([Ph2NH2]OTf) and reductant ((C6H6)2Cr), with turnover as high as 73 demonstrated. This catalyst system is also modestly competent for N2R and structurally related to other tris(phosphine)Fe-based N2R catalysts. The choice of catalyst and reductant is important to observe high yields. Mechanistic studies elucidate several intermediates of CN- reduction, including iron isocyanides (P3SiFeCNH+/0) and terminal iron aminocarbynes (P3SiFeCNH2+/0). Aminocarbynes are isoelectronic to iron hydrazidos (Fe═N-NH2+/0), which have been invoked as selectivity-determining intermediates of N2R (NH3 versus N2H4 products). For the present CN- reduction catalysis, reduction of aminocarbyne P3SiFeCNH2+ is proposed to be rate but not selectivity contributing. Instead, by comparison with the reactivity of a methylated aminocarbyne analogue (P3SiFeCNMe2), and associated computational studies, formation of a Fischer carbene (P3SiFeC(H)(NH2)+) intermediate that is on path for either CH4 and NH3 (6 e-) or CH3NH2 (4 e-) products is proposed. From this carbene intermediate, pathways to the observed CH4 and NH3 products (distinct from CH3NH2 formation) are considered to compare and contrast the (likely) mechanism/s of CN- and N2 reduction.

Molecular Additives Improve the Selectivity of CO2 Photoelectrochemical Reduction over Gold Nanoparticles on Gallium Nitride.

Photoelectrochemical CO2 reduction (CO2R) is an appealing solution for converting carbon dioxide into higher-value products. However, CO2R in aqueous electrolytes suffers from poor selectivity due to the competitive hydrogen evolution reaction that is dominant on semiconductor surfaces in aqueous electrolytes. We demonstrate that functionalizing gold/p-type gallium nitride devices with a film derived from diphenyliodonium triflate suppresses hydrogen generation from 90% to 18%. As a result, we observe increases in the Faradaic efficiency and partial current density for carbon monoxide of 50% and 3-fold, respectively. Furthermore, we demonstrate through optical absorption measurements that the molecular film employed herein, regardless of thickness, does not affect the photocathode's light absorption. Altogether, this study provides a rigorous platform for elucidating the catalytic structure-property relationships to enable engineering of active, stable, and selective materials for photoelectrochemical CO2R.

Highly Selective Fe-Catalyzed Nitrogen Fixation to Hydrazine Enabled by Sm(II) Reagents with Tailored Redox Potential and pKa.

Controlling product selectivity in multiproton, multielectron reductions of unsaturated small molecules is of fundamental interest in catalysis. For the N2 reduction reaction (N2RR) in particular, parameters that dictate selectivity for either the 6H+/6e- product ammonia (NH3) or the 4H+/4e- product hydrazine (N2H4) are poorly understood. To probe this issue, we have developed conditions to invert the selectivity of a tris(phosphino)borane iron catalyst (Fe), with which NH3 is typically the major product of N2R, to instead favor N2H4 as the sole observed fixed-N product (>99:1). This dramatic shift is achieved by replacing moderate reductants and strong acids with a very strongly reducing but weakly acidic SmII-(2-pyrrolidone) core supported by a hexadentate dianionic macrocyclic ligand (SmII-PH) as the net hydrogen-atom donor. The activity and efficiency of the catalyst with this reagent remain high (up to 69 equiv of N2H4 per Fe and 67% fixed-N yield per H+). However, by generating N2H4 as the kinetic product, the overpotential of this Sm-driven reaction is 700 mV lower than that of the mildest reported set of NH3-selective conditions with Fe. Mechanistic data support assignment of iron hydrazido(2-) species FeNNH2 as selectivity-determining: we infer that protonation of FeNNH2 at Nß, favored by strong acids, releases NH3, whereas one-electron reduction to FeNNH2-, favored by strong reductants such as SmII-PH, produces N2H4 via reactivity initiated at Nα. Spectroscopic data also implicate a role for SmIII-binding to anionic FeN2- (via an Fe-N2- -SmIII species) with respect to catalytic efficacy.

Advancing electrocatalytic nitrogen fixation: insights from molecular systems.

Nitrogen fixation has a rich history within the inorganic chemistry community. In recent years attention has (re)focused on developing electrocatalytic systems capable of mediating the nitrogen reduction reaction (N2RR). Well-defined molecular catalyst systems have much to offer in this context. This personal perspective summarizes recent progress from our laboratory at Caltech, pulling together lessons learned from a number of studies we have conducted, placing them within the broader context of thermodynamic efficiency and selectivity for the N2RR. In particular, proton-coupled electron transfer (PCET) provides an attractive strategy to achieve enhanced efficiency for the multi-electron/proton reduction of N2 to produce NH3 (or NH4+), and electrocatalytic PCET (ePCET) via an ePCET mediator affords a promising means of mitigating HER such that the N2RR can be achieved in a catalytic fashion.

Light Alters the NH3 vs N2 H4 Product Profile in Iron-catalyzed Nitrogen Reduction via Dual Reactivity from an Iron Hydrazido (Fe=NNH2 ) Intermediate.

Whereas synthetically catalyzed nitrogen reduction (N2 R) to produce ammonia is widely studied, catalysis to instead produce hydrazine (N2 H4 ) has received less attention despite its considerable mechanistic interest. Herein, we disclose that irradiation of a tris(phosphine)borane (P3 B ) Fe catalyst, P3 B Fe+ , significantly alters its product profile to increase N2 H4 versus NH3 ; P3 B Fe+ is otherwise known to be highly selective for NH3 . We posit a key terminal hydrazido intermediate, P3 B Fe=NNH2 , as selectivity-determining. Whereas its singlet ground state undergoes protonation to liberate NH3 , a low-lying triplet excited state leads to reactivity at Nα and formation of N2 H4 . Associated electrochemical and spectroscopic studies establish that N2 H4 lies along a unique product pathway; NH3 is not produced from N2 H4 . Our findings are distinct from the canonical mechanism for hydrazine formation, which proceeds via a diazene (HN=NH) intermediate and showcase light as a tool to tailor selectivity.

Organic Additive-derived Films on Cu Electrodes Promote Electrochemical CO2 Reduction to C2+ Products Under Strongly Acidic Conditions.

Electrochemical CO2 reduction (CO2 R) at low pH is desired for high CO2 utilization; the competing hydrogen evolution reaction (HER) remains a challenge. High alkali cation concentration at a high operating current density has recently been used to promote electrochemical CO2 R at low pH. Herein we report an alternative approach to selective CO2 R (>70 % Faradaic efficiency for C2+ products, FEC2+ ) at low pH (pH 2; H3 PO4 /KH2 PO4 ) and low potassium concentration ([K+ ]=0.1 M) using organic film-modified polycrystalline copper (Modified-Cu). Such an electrode effectively mitigates HER due to attenuated proton transport. Modified-Cu still achieves high FEC2+ (45 % with Cu foil /55 % with Cu GDE) under 1.0 M H3 PO4 (pH≈1) at low [K+ ] (0.1 M), even at low operating current, conditions where HER can otherwise dominate.

Electrocatalytic Nitrogen Reduction on a Molybdenum Complex Bearing a PNP Pincer Ligand.

Electrocatalytic nitrogen reduction (N2R) mediated by well-defined molecular catalysts is poorly developed by comparison with other reductive electrocatalytic transformations. Herein, we explore the viability of electrocatalytic N2R mediated by a molecular Mo-PNP complex. A careful choice of acid, electrode material, and electrolyte mitigates electrode-mediated HER under direct electrolysis and affords up to 11.7 equiv of NH3 (Faradaic efficiency < 43%) at -1.89 V versus Fc+/Fc. The addition of a proton-coupled electron transfer (PCET) mediator has no effect. The data presented are rationalized by an initial electron transfer (ET) that sets the applied bias needed and further reveal an important impact of [Mo] concentration, thereby pointing to potential bimolecular steps (e.g., N2 splitting) as previously proposed during chemically driven N2R catalysis. Finally, facile reductive protonation of [Mo(N)Br(HPNP)] with pyridinium acids is demonstrated.

Sm(II)-Mediated Proton-Coupled Electron Transfer: Quantifying Very Weak N-H and O-H Homolytic Bond Strengths and Factors Controlling Them.

Coordination of alcohols to the single-electron reductant samarium diiodide (SmI2) results in substantial O-H bond weakening, affording potent proton-coupled electron transfer (PCET) reagents. However, poorly defined speciation of SmI2 in tetrahydrofuran (THF)/alcohol mixtures limits reliable thermodynamic analyses of such systems. Rigorous determination of bond dissociation free energy (BDFE) values in such Sm systems, important to evaluating their reactivity profiles, motivates studies of model Sm systems where contributing factors can be teased apart. Here, a bulky and strongly chelating macrocyclic ligand ((tBu2ArOH)2Me2cyclam) maintains solubility, eliminates dimerization pathways, and facilitates clean electrochemical behavior in a well-defined functional model for the PCET reactivity of SmII with coordinating proton sources. Direct measurement of thermodynamic parameters enables reliable experimental estimation of the BDFEs in 2-pyrrolidone and MeOH complexes of ((tBu2ArO)2Me2cyclam)SmII, thereby revealing exceptionally weak N-H and O-H BDFEs of 27.2 and <24.1 kcal mol-1, respectively. Expanded thermochemical cycles reveal that this bond weakening stems from the very strongly reducing SmII center and the formation of strong SmIII-alkoxide (and -pyrrolidonate) interactions in the PCET products. We provide a detailed analysis comparing these BDFE values with those that have been put forward for SmI2 in THF in the presence of related proton donors. We suggest that BDFE values for the latter systems may in fact be appreciably higher than the system described herein. Finally, protonation and electrochemical reduction steps necessary for the regeneration of the PCET donors from SmIII-alkoxides are demonstrated, pointing to future strategies aimed at achieving (electro)catalytic turnover using SmII-based PCET reagents.

Use of a PCET Mediator Enables a Ni-HER Electrocatalyst to Act as a Hydride Delivery Agent.

The generation of metal hydride intermediates during reductive electrocatalysis in the presence of acid most commonly leads to the hydrogen evolution reaction (HER). Redirecting the reactivity profile of such hydride intermediates toward the reduction of unsaturated substrates is an exciting opportunity in catalysis but presents a challenge in terms of catalyst selectivity. In this study, we demonstrate that a prototypical phosphine-supported Ni-HER catalyst can be repurposed toward the electrocatalytic reduction of a model substrate, methyl phenylpropiolate, via hydride transfer from a NiII-H when interfaced with a metallocene-derived proton-coupled electron transfer (PCET) mediator. Key to success is generation of the NiII-H at a potential pinned to that of the PCET mediator which is appreciably anodic of the onset of HER. Electrochemical, spectroscopic, and theoretical data point to a working mechanism where a PCET step from the metallocene-derived mediator to NiII generates NiIII-H and is rate-determining; the latter NiIII-H is then readily reduced to a NiII-H, which is competent for substrate reduction. Additional studies show that this tandem PCET-mediated hydride generation can afford high stereoselectivity (e.g., >20:1 Z/E using a phosphine-cobalt precatalyst with ethyl 2-heptynoate) and can also be used for the reduction of α,ß-unsaturated ketones.

Catalytic transfer hydrogenation of N2 to NH3 via a photoredox catalysis strategy.

Inspired by momentum in applications of reductive photoredox catalysis to organic synthesis, photodriven transfer hydrogenations toward deep (>2 e-) reductions of small molecules are attractive compared to using harsh chemical reagents. Noteworthy in this context is the nitrogen reduction reaction (N2RR), where a synthetic photocatalyst system had yet to be developed. Noting that a reduced Hantzsch ester (HEH2) and related organic structures can behave as 2 e-/2 H+ photoreductants, we show here that, when partnered with a suitable catalyst (Mo) under blue light irradiation, HEH2 facilitates delivery of successive H2 equivalents for the 6 e-/6 H+ catalytic reduction of N2 to NH3; this catalysis is enhanced by addition of a photoredox catalyst (Ir). Reductions of additional substrates (nitrate and acetylene) are also described.

Characterization of a Proposed Terminal Iron(III) Nitride Intermediate of Nitrogen Fixation Stabilized by a Trisphosphine-Borane Ligand.

Terminal iron nitrides (Fe≡N) have been proposed as intermediates of Fe-mediated nitrogen fixation, and well-defined synthetic iron nitrides have been characterized in high oxidation states, including FeIV , FeV , and FeVI . This study reports the generation and low temperature characterization of a terminally bound iron(III) nitride, P3 B Fe(N) (P3 B =tris(o-diisopropylphosphinophenyl)borane), which is a proposed intermediate of iron-mediated nitrogen fixation by the P3 B Fe-catalyst system. CW- and pulse EPR spectroscopy (HYSCORE and ENDOR), supported by DFT calculations, help to define a 2 A ground state electronic structure of this C3 -symmetric nitride species, placing the unpaired spin in a sigma orbital along the B-Fe-N vector; this electronic structure is distinct for an iron nitride. The unusual d5 -configuration is stabilized by significant delocalization (≈50 %) of the unpaired electron onto the axial boron and nitrogen ligands, with a majority of the spin residing on boron.