Six-electron Reduction Research Articles

The Electrochemistry of Nitro Compounds from a Bibliometric Approach

The heterocyclic and aromatic nitro compounds are industrially and commercially important chemicals, used in drugs, explosives, pesticides, and dyes. Despite their economic importance, the advent of these chemicals also brought serious human health and environmental problems due to their toxic characteristics as contaminants and pollutants. The nitro group is catalyzed in vivo by nitroreductases promoting a six-electron reduction to form sequentially the nitro radical anion, nitroso-, N-hydroxylamino and amino-functional groups. These reactions can be electrochemically reproduced, involving the development of analytical methods and electrochemical sensors, degradation and removal of organic compounds in effluents, corrosion studies, and studies of action mechanism of drugs on DNA bases. In this sense, a bibliometric analysis has been performed based on the Web of Science Core Collection in conjunction with VOSviewer software for generating network visualizations. This research covered the database until 2023, describing the main research areas and the annual publication trends, the collaborations and contributions among countries and research institutions, in addition to identifying the most cited articles, hotspots, and the analysis of evolution and relevance of keywords. This investigation made it possible to recognize the main research focuses and what is under development, providing a comprehensive overview on electrochemistry of nitro compounds.

Proton-Coupled Electron Transfer Mechanisms for CO2 Reduction to Methanol Catalyzed by Surface-Immobilized Cobalt Phthalocyanine.

Immobilized cobalt phthalocyanine (CoPc) is a highly promising architecture for the six-proton, six-electron reduction of CO2 to methanol. This electroreduction process relies on proton-coupled electron transfer (PCET) reactions that can occur by sequential or concerted mechanisms. Immobilization on a conductive support such as carbon nanotubes or graphitic flakes can fundamentally alter the PCET mechanisms. We use density functional theory (DFT) calculations of CoPc adsorbed on an explicit graphitic surface model to investigate intermediates in the electroreduction of CO2 to methanol. Our calculations show that the alignment of the CoPc and graphitic electronic states influences the reductive chemistry. These calculations also distinguish between charging the graphitic surface and reducing the CoPc and adsorbed intermediates as electrons are added to the system. This analysis allows us to identify the chemical transformations that are likely to be concerted PCET, defined for these systems as the mechanism in which protonation of a CO2 reduction intermediate is accompanied by electron abstraction from the graphitic surface to the adsorbate without thermodynamically stable intermediates. This work establishes a mechanistic pathway for methanol production that is consistent with experimental observations and provides fundamental insight into how immobilization of the CoPc impacts its CO2 reduction chemistry.

Reaction Mechanism Catalyzed by the Dissimilatory Sulfite Reductase - The Role of the Siroheme-[4FeS4] Cofactor.

The present work is another part of our investigation on the pathway of dissimilatory sulfate reduction and covers a theoretical study on the reaction catalyzed by dissimilatory sulfite reductase (dSIR). dSIR is the terminal enzyme involved in this metabolic pathway, which uses the siroheme-[4Fe4S] cofactor for six-electron reduction of sulfite to sulfide. In this study we use a large cluster model containing siroheme-[4Fe4S] cofactor and protein residues involved in the direct interactions with the substrate, to get insight into the most feasible reaction mechanism and to understand the role of each considered active site component. In combination with earlier studies reported in the literature, our results lead to several interesting insights. One of the most important conclusions is that the reaction mechanism consists of three steps of two-electron reduction of sulfur and the probable role of the siroheme-[4Fe4S] cofactor is to ensure the delivery of packages of two electrons to the reactant.

Ultrathin, Cationic Covalent Organic Nanosheets for Enhanced CO2 Electroreduction to Methanol.

Metalloporphyrins and metallophthalocyanines emerge as popular building blocks to develop covalent organic nanosheets (CONs) for CO2 reduction reaction (CO2RR). However, existing CONs predominantly yield CO, posing a challenge in achieving efficient methanol production through multielectron reduction. Here, ultrathin, cationic, and cobalt-phthalocyanine-based CONs (iminium-CONs) are reported for electrochemical CO2-to-CH3OH conversion. The integration of quaternary iminium groups enables the formation of ultrathin morphology with uniformly anchored cobalt active sites, which are pivotal for facilitating rapid multielectron transfer. Moreover, the cationic iminium-CONs exhibit a lower activity for hydrogen evolution side reaction. Consequently, iminium-CONs manifest significantly enhanced selectivity for methanol production, as evidenced by a remarkable 711% and 270% improvement in methanol partial current density (jCH3OH) compared to pristine CoTAPc and neutral imine-CONs, respectively. Under optimized conditions, iminium-CONs deliver a high jCH3OH of 91.7 mA cm-2 at -0.78 V in a flow cell. Further, iminium-CONs achieve a global methanol Faradaic efficiency (FECH3OH) of 54% in a tandem device. Thanks to the single-site feature, the methanol is produced without the concurrent generation of other liquid byproducts. This work underscores the potential of cationic covalent organic nanosheets as a compelling platform for electrochemical six-electron reduction of CO2 to methanol.

Trimer Quinoxalines as Organic Cathode Materials for Lithium-Ion Batteries

Due to synthetic ease, high redox potentials, low solubility in polar electrolytes, and good electric conductivity of their semiconducting crystals, discotic quinoxaline trimers (3Q) have been considered as possible candidates for 4 V organic cathodes in lithium-ion batteries. To assess their feasibility as such materials, several 3Q derivatives have been synthesized and tested in half-cells. In voltage limited cycling tests at 1.2–3.9 V vs Li/Li+, the specific discharge capacities of 40–180 mAh g−1 were obtained at a rate of 1 C, and multiple lithiation of 3Q and its derivatives was observed during discharge. However, the obtained discharge capacity was only a fraction of the theoretical capacity expected for reversible six-electron reduction; there was also rapid capacity fade. Our spectroscopic studies indicate the reversible three-electron lithiation at 2 V vs Li/Li+, but suggest instability of more highly discharged states. Our conclusion is that while the 3Q derivatives combine several traits that are desirable in an organic cathode material (including negligible solubility, capacity for multiple charging, and near-100% coulombic efficiency), these materials are still impractical to use.

Domain crossover in the reductase subunit of NADPH-dependent assimilatory sulfite reductase

NADPH-dependent assimilatory sulfite reductase (SiR) from Escherichia coli performs a six-electron reduction of sulfite to the bioavailable sulfide. SiR is composed of a flavoprotein (SiRFP) reductase subunit and a hemoprotein (SiRHP) oxidase subunit. There is no known high-resolution structure of SiR or SiRFP, thus we do not yet fully understand how the subunits interact to perform their chemistry. Here, we used small-angle neutron scattering to understand the impact of conformationally restricting the highly mobile SiRFP octamer into an electron accepting (closed) or electron donating (open) conformation, showing that SiR remains active, flexible, and asymmetric even with these conformational restrictions. From these scattering data, we model the first solution structure of SiRFP. Further, computational modeling of the N-terminal 52 amino acids that are responsible for SiRFP oligomerization suggests an eight-helical bundle tethers together the SiRFP subunits to form the SiR core. Finally, mass spectrometry analysis of the closed SiRFP variant show that SiRFP is capable of inter-molecular domain crossover, in which the electron donating domain from one polypeptide is able to interact directly with the electron accepting domain of another polypeptide. This structural characterization suggests that SiR performs its high-volume electron transfer through both inter- and intramolecular pathways between SiRFP domains and, thus, cis or trans transfer from reductase to oxidase subunits. Such highly redundant potential for electron transfer makes this system a potential target for designing synthetic enzymes.

Understanding the effects of higher-order assembly on the structure of the sulfite reductase.

The redox state of sulfur determines its bioavailbility and its reduction to sulfide is required for assimilation of sulfur into amino acids and cofactors.The NADPH-dependent assimilatory sulfite reductase (SiR) is a metabolic enzyme that performs the six-electron reduction of sulfite to sulfide. Escherichia coli SiR is composed of eight flavoprotein (SiRFP, ⍺) and four hemoprotein (SiRHP, β) subunits that associate in α8:β4 holoenzyme. This dodecameric assembly is unique because SiRs from other sulfur reducing organisms are dimers of reductase and oxidase subunits. Both SiR subunits are modular. SiRFP is a fusion between flavodoxin domain and a ferredoxin-NADP+ reductase domain that assembles through its 52 N-terminal amino acids into an octamer. SiRHP is a monomeric metalloenzyme that houses the active site. Despite almost 30 years of effort across many laboratories, structures of SiR complexes have remained recalcitrant to X-ray crystallography and cryo-EM because of its structural heterogeneity aising from intrinsically disordered regions throughout the complex, including the flexible linker joining SiRFP's flavin binding domain. Thus we do not know how the domains assemble, which leaves a gap in understanding about how these domains coordinate to perform electron transfer. Here, we use neutron contrast variation (NCV) and small angle neutron scattering (SANS) to observe the relative subunit positioning within the SiR complex. To better understand the electron transfer mechanism, we have generated conformationally restricted variant of SiRFP that either locks its flavin binding domains in an open conformation by shortening the linker between domains, or in closed conformation by engineering disulfide bonds. SANS and NCV study reveal SiR's asymmetric complex, and the resulting maps supports a redundant, cis/trans mechanism of electron transfer between the reductase subunits as well as between the tightly or transiently bound reductase and oxidase domains.

An unusual active site architecture in cytochrome c nitrite reductase NrfA-1 from Geobacter metallireducens.

Dissimilatory nitrate reduction to ammonia (DNRA) is a central pathway in the biogeochemical nitrogen cycle, allowing for the utilisation of nitrate or nitrite as terminal electron acceptors. In contrast to the competing denitrification to N2, a major part of the essential nutrient nitrogen in DNRA is retained within the ecosystem and made available as ammonium to serve as a nitrogen source for other organisms. The second step of DNRA is mediated by the pentahaem cytochrome c nitrite reductase NrfA that catalyses the six-electron reduction of nitrite to ammonium and is widely distributed among bacteria. A recent crystal structure of a NrfA ortholog from Geobacter lovleyi was the first characterised representative of a novel subclass of NrfA enzymes that lacked the canonical Ca2+ ion close to the active site haem 1. Here we report the structural and functional characterisation of NrfA from the closely related Geobacter metallireducens. We established the recombinant production of catalytically active NrfA with its unique, lysine-coordinated active site haem heterologously in Escherichia coli and determined its three-dimensional structure by X-ray crystallography to 1.9Å resolution. The structure confirmed GmNrfA as a further calcium-independent NrfA protein, and it also shows an altered active site that contained an unprecedented aspartate residue, D80, close to the substrate-binding site. This residue formed part of a loop that also caused a changed arrangement of the conserved substrate/product channel relative to other NrfA proteins and rendered the protein insensitive to the inhibitor sulphate. To elucidate the relevance of D80, we produced and studied the variants D80A and D80N that showed significantly reduced catalytic activity.

AgAu Hollow Hexagonal Nanoplates for Ultrasensitive Tracking of Pesticides and Plasmonic Photocatalysis by Surface-Enhanced Raman Spectroscopy

Plasmonic metal nanostructures have been attracting great interest due to their unique optical and catalytic properties. Here, we report a simple and mild synthetic approach for the colloidal synthesis of AgAu hollow hexagonal nanoplates (AgAu HHNPs) with multitips through the careful choice of suitable reducing agents. In particular, when a relatively stronger reducing agent (e.g., ascorbic acid, AA) is employed, the deposition rate of Ag and Au adatoms on the walls is faster than the rate of outward diffusion rate of Ag atoms inside Ag nanoplates. This causes more Ag and Au adatoms to be diffused toward the tips of AgAu HHNPs. Interestingly, well-defined AgAu HHNP nanostructures with controlled multitips possess an enhanced localized electromagnetic field due to the tip effect. The produced nanomaterial exhibits sensitive trace detection of the pesticide residue by means of the surface-enhanced Raman spectroscopy (SERS) technique, in which the limit of detection (LOD) of rhodamine 6G is 10–13 M and the LOD of tetramethylthiuram disulfide (TMTD) is 10–9 M. Furthermore, it also shows a particularly high reaction rate for the six-electron reduction of p-nitrothiophenol to p-aminothiophenol on AgAu HHNPs. The entire reaction processes have been in situ monitored by SERS, revealing that molecular hydrogen in situ generated on the semiconductor AgCl dominates the plasmonic photocatalysis. The detailed understanding gained herein will help to disentangle the rational design mechanism of complex hollow nanostructures, as well as the relationship between structural configuration and resulting performance in SERS detection and plasmonic photocatalysis.

Aqueous Photoelectrochemical CO2 Reduction to CO and Methanol over a Silicon Photocathode Functionalized with a Cobalt Phthalocyanine Molecular Catalyst.

We report a precious-metal-free molecular catalyst-based photocathode that is active for aqueous CO2 reduction to CO and methanol. The photoelectrode is composed of cobalt phthalocyanine molecules anchored on graphene oxide which is integrated via a (3-aminopropyl)triethoxysilane linker to p-type silicon protected by a thin film of titanium dioxide. The photocathode reduces CO2 to CO with high selectivity at potentials as mild as 0 V versus the reversible hydrogen electrode (vs RHE). Methanol production is observed at an onset potential of -0.36 V vs RHE, and reaches a peak turnover frequency of 0.18 s-1 . To date, this is the only molecular catalyst-based photoelectrode that is active for the six-electron reduction of CO2 to methanol. This work puts forth a strategy for interfacing molecular catalysts to p-type semiconductors and demonstrates state-of-the-art performance for photoelectrochemical CO2 reduction to CO and methanol.

Highly Strained Arene-Fused 1,2-Diborete Biradicaloid.

The stepwise reduction of a doubly cyclic alkyl(amino)carbene (CAAC)-stabilized 2,3-bis(dibromoboryl)naphthalene enables the isolation of the corresponding mono- and bis(boryl) radicals (one- and two-electron reduction), a 2π-aromatic 1,2-diborete (four-electron reduction), which shows biradical character in the solid-state EPR spectrum, and its cyclic bis(alkylidene)diboron dianion (six-electron reduction). The X-ray crystallographic analysis of the diborete shows a highly strained and twisted four-membered ring with a formal cis-diborene motif featuring a very elongated B-B double bond. Calculations based on DFT and multireference approaches reveal that the diborete possesses an open-shell singlet biradicaloid ground state, which is slightly energetically preferred to its EPR-active triplet-state congener. The addition of CO to the diborete resulted in B-B bond splitting and the formation of the corresponding closed-shell singlet, doubly Lewis base-stabilized bis(borylene), whereas a twofold γ insertion of phenyl azide generates a 1,3-bis(diazenyl)-1,3,2,4-diazadiboretidine.

Nitroreduction: A Critical Metabolic Pathway for Drugs, Environmental Pollutants, and Explosives.

Nitro group containing xenobiotics include drugs, cancer chemotherapeutic agents, carcinogens (e.g., nitroarenes and aristolochic acid) and explosives. The nitro group undergoes a six-electron reduction to form sequentially the nitroso-, N-hydroxylamino- and amino-functional groups. These reactions are catalyzed by nitroreductases which, rather than being enzymes with this sole function, are enzymes hijacked for their propensity to donate electrons to the nitro group either one at a time via a radical mechanism or two at time via the equivalent of a hydride transfer. These enzymes include: NADPH-dependent flavoenzymes (NADPH: P450 oxidoreductase, NAD(P)H-quinone oxidoreductase), P450 enzymes, oxidases (aldehyde oxidase, xanthine oxidase) and aldo-keto reductases. The hydroxylamino group once formed can undergo conjugation reactions with acetate or sulfate catalyzed by N-acetyltransferases or sulfotransferases, respectively, leading to the formation of intermediates containing a good leaving group which in turn can generate a nitrenium or carbenium ion for covalent DNA adduct formation. The intermediates in the reduction sequence are also prone to oxidation and produce reactive oxygen species. As a consequence, many nitro-containing xenobiotics can be genotoxic either by forming stable covalent adducts or by oxidatively damaging DNA. This review will focus on the general chemistry of nitroreduction, the enzymes responsible, the reduction of xenobiotic substrates, the regulation of nitroreductases, the ability of nitrocompounds to form DNA adducts and act as mutagens as well as some future directions.

(n-Bu)4NBr-Promoted N2 Splitting to Molybdenum Nitride.

Splitting of N2 via six-electron reduction and further functionalization to value-added products is one of the most important and challenging chemical transformations in N2 fixation. However, most N2 splitting approaches rely on strong chemical or electrochemical reduction to generate highly reactive metal species to bind and activate N2, which is often incompatible with functionalizing agents. Catalytic and sustainable N2 splitting to produce metal nitrides under mild conditions may create efficient and straightforward methods for N-containing organic compounds. Herein, we present that a readily available and nonredox (n-Bu)4NBr can promote N2-splitting with a Mo(III) platform. Both experimental and theoretical mechanistic studies suggest that simple X- (X = Br, Cl, etc.) anions could induce the disproportionation of MoIII[N(TMS)Ar]3 at the early stage of the catalysis to generate a catalytically active {MoII[N(TMS)Ar]3}- species. The quintet MoII species prove to be more favorable for N2 fixation kinetically and thermodynamically, compared with the quartet MoIII counterpart. Especially, computational studies reveal a distinct heterovalent {MoII-N2-MoIII} dimeric intermediate for the N≡N triple bond cleavage.

Coordination and Homologation of CO at Al(I): Mechanism and Chain Growth, Branching, Isomerization, and Reduction.

Homologation of carbon monoxide is central to the heterogeneous Fischer–Tropsch process for the production of hydrocarbon fuels. C–C bond formation has been modeled by homogeneous systems, with [CnOn]2– fragments (n = 2–6) formed by two-electron reduction being commonly encountered. Here, we show that four- or six-electron reduction of CO can be accomplished by the use of anionic aluminum(I) (“aluminyl”) compounds to give both topologically linear and branched C4/C6 chains. We show that the mechanism for homologation relies on the highly electron-rich nature of the aluminyl reagent and on an unusual mode of interaction of the CO molecule, which behaves primarily as a Z-type ligand in initial adduct formation. The formation of [C6O6]4– from [C4O4]4– shows for the first time a solution-phase CO homologation process that brings about chain branching via complete C–O bond cleavage, while a comparison of the linear [C4O4]4– system with the [C4O4]6– congener formed under more reducing conditions models the net conversion of C–O bonds to C–C bonds in the presence of additional reductants.

Heterometallic Clusters with Uranium-Metal Bonds Supported by Double-Layer Nitrogen-Phosphorus Ligands.

ConspectusHeterometallic clusters with M-M bonds have significantly interested chemists because of their attractive structures and synergistic effects in small-molecule activation and catalysis. However, reports of the isolation of heterometallic clusters with uranium-transition metal (U-TM) bonds remain very limited. In this Account, we describe our research in the construction of heterometallic molecular clusters with multiple U-TM single or multiple bonds supported by novel double-layer N-P ligands. Multimetallic synergistic catalysis and small-molecule activation with these species are also summarized.First, according to the hard-soft acid-base theory, we employed a three-armed N-P ligand, which can be used to construct heterometallic clusters with four or six U-Ni bonds. This strategy was also effective in the construction of complexes with direct rare earth metal-TM bonding. The similar two-armed N-P ligands also are effective platforms for the synthesis of heterometallic complexes with U-Ni, U-Pd, and U-Pt bonds.Second, a set of heterometallic clusters featuring U≡Rh, U≡Co, and U≡Fe triple bonds were constructed under routine experimental conditions. X-ray diffraction analysis of these clusters exhibits the shortest U-TM bond distance (1.9693(4) Å for the U≡Fe triple bond) in these complexes. Theoretical studies reveal that the nature of the triple bond is one covalent σ bond and two TM → U dative π bonds. A large Wiberg bond index (WBI) of 2.93 and a significant degree of covalency for the U≡TM triple bonds were also found in these complexes.Third, these uranium complexes supported by the double-layer N-P ligands exhibit great potential in small-molecule activation. For instance, N2 cleavage without an external reducing agent was achieved by a U(III)-P(III) synergistic six-electron reduction. The synergism between U(III) and P(III) enables the activation of other small molecules, such as O2, P4, and As0(nano), and highlights the importance of the P atom in the double-layer N-P ligand for the activation of small molecules. A heterometallic cluster with U-Rh bonds can break the strong N≡N triple bond in N2 in the presence of potassium graphite, suggesting a synergistic effect between U and Rh. This multimetallic synergistic effect was also observed in catalytic processes. A heterometallic cluster with U≡Co triple bonds shows excellent selectivity and activity in the hydroboration of a series of alkynes under mild conditions. These results lead to effective methods for the construction of heterometallic molecular clusters with U-TM single or multiple bonds and could promote the application of heterometallic clusters with U-TM bonds in catalysis and the activation of small molecules.

Six-Electron Reduction of LiIO3 to LiOH in Aprotic Solvents and Implications for Li–O2 Batteries

Six-Electron Reduction of LiIO₃ to LiOH in Aprotic Solvents and Implications for Li–O₂ Batteries

Neutron scattering maps the higher-order assembly of NADPH-dependent assimilatory sulfite reductase

Precursor molecules for biomass incorporation must be imported into cells and made available to the molecular machines that build the cell. Sulfur-containing macromolecules require that sulfur be in its S2− oxidation state before assimilation into amino acids, cofactors, and vitamins that are essential to organisms throughout the biosphere. In α-proteobacteria, NADPH-dependent assimilatory sulfite reductase (SiR) performs the final six-electron reduction of sulfur. SiR is a dodecameric oxidoreductase composed of an octameric flavoprotein reductase (SiRFP) and four hemoprotein metalloenzyme oxidases (SiRHPs). SiR performs the electron transfer reduction reaction to produce sulfide from sulfite through coordinated domain movements and subunit interactions without release of partially reduced intermediates. Efforts to understand the electron transfer mechanism responsible for SiR’s efficiency are confounded by structural heterogeneity arising from intrinsically disordered regions throughout its complex, including the flexible linker joining SiRFP’s flavin-binding domains. As a result, high-resolution structures of SiR dodecamer and its subcomplexes are unknown, leaving a gap in the fundamental understanding of how SiR performs this uniquely large-volume electron transfer reaction. Here, we use deuterium labeling, in vitro reconstitution, analytical ultracentrifugation (AUC), small-angle neutron scattering (SANS), and neutron contrast variation (NCV) to observe the relative subunit positions within SiR’s higher-order assembly. AUC and SANS reveal SiR to be a flexible dodecamer and confirm the mismatched SiRFP and SiRHP subunit stoichiometry. NCV shows that the complex is asymmetric, with SiRHP on the periphery of the complex and the centers of mass between SiRFP and SiRHP components over 100 Å apart. SiRFP undergoes compaction upon assembly into SiR’s dodecamer and SiRHP adopts multiple positions in the complex. The resulting map of SiR’s higher-order structure supports a cis/trans mechanism for electron transfer between domains of reductase subunits as well as between tightly bound or transiently interacting reductase and oxidase subunits.

Uranium(III)–Phosphorus(III) Synergistic Activation of White Phosphorus and Arsenic

Uranium(III)–Phosphorus(III) Synergistic Activation of White Phosphorus and Arsenic

Heterogeneous Molecular Catalysts of Metal Phthalocyanines for Electrochemical CO2 Reduction Reactions.

ConspectusMolecular catalysts, often deployed in homogeneous conditions, are favorable systems for structure-reactivity correlation studies of electrochemical reactions because of their well-defined active site structures and ease of mechanistic investigation. In pursuit of selective and active electrocatalysts for the CO2 reduction reactions which are promising for converting carbon emissions to useful fuels and chemical products, it is desirable to support molecular catalysts on substrates because heterogeneous catalysts can afford the high current density and operational convenience that practical electrolyzers require. Herein, we share our understanding in the development of heterogenized metal phthalocyanine catalysts for the electrochemical reduction of CO2. From the optimization of preparation methods and material structures for the electrocatalytic activity toward CO2 reduction to CO, we find that molecular-level dispersion of the active material and high electrical conductivity of the support are among the most important factors controlling the activity. The molecular nature of the active site enables mechanism-based optimization. We demonstrate how electron-withdrawing and -donating ligand substituents can be utilized to modify the redox property of the molecule and improve its catalytic activity and stability. Adjusting these factors further allows us to achieve electrochemical reduction of CO2 to methanol with appreciable activity, which has not been attainable by conventional molecular catalysts. The six-electron reduction process goes through CO as the key intermediate. Rapid and continuous electron delivery to the active site favors further reduction of CO to methanol. We also point out that, in homogeneous electrocatalysis where the catalyst molecules are dissolved in the electrolyte solution, even if the molecular structure remains intact, the actual catalysis may be dominated by molecules permanently adsorbed on the electrode surface and is thus heterogeneous in nature. This account uses our research on CO2 electroreduction reactions catalyzed by metal phthalocyanine molecules to illustrate our understanding about heterogeneous molecular electrocatalysis, which is also applicable to other electrochemical systems.

Facile Dinitrogen and Dioxygen Cleavage by a Uranium(III) Complex: Cooperativity Between the Non-Innocent Ligand and the Uranium Center.

Activation of dinitrogen (N2 , 78 %) and dioxygen (O2 , 21 %) has fascinated chemists and biochemists for decades. The industrial conversion of N2 into ammonia requires extremely high temperatures and pressures. Herein we report the first example of N2 and O2 cleavage by a uranium complex, [N(CH2 CH2 NPi Pr2 )3 U]2 (TMEDA), under ambient conditions without an external reducing agent. The N2 triple bond breaking implies a UIII -PIII six-electron reduction. The hydrolysis of the N2 reduction product allows the formation of ammonia or nitrogen-containing organic compounds. The interaction between UIII and PIII in this molecule allows an eight-electron reduction of two O2 molecules. This study establishes that the combination of uranium and a low-valent nonmetal is a promising strategy to achieve a full N2 and O2 cleavage under ambient conditions, which may aid the design of new systems for small molecules activation.