Catalytic defluorinative ketyl–olefin coupling by halogen-atom transfer

Ketyl–olefin coupling reactions stand as one of the fundamental chemical transformations in synthetic chemistry and have been widely employed in the generation of complex molecular architectures and natural product synthesis. However, catalytic ketyl–olefin coupling, until the recent development of photoredox chemistry and electrosynthesis through single-electron transfer mechanisms, has remained largely undeveloped. Herein, we describe a new approach to achieve catalytic ketyl–olefin coupling reactions by a halogen-atom transfer mechanism, which provides innovative and efficient access to various gem-difluorohomoallylic alcohols under mild conditions with broad substrate scope. Preliminary mechanistic experimental and computational studies demonstrate that this radical-to-polar crossover transformation could be achieved by sequentially orchestrated Lewis acid activation, halogen-atom transfer, radical addition, single-electron reduction and β-fluoro elimination.

A catalytic ketyl–olefin coupling reaction including sequentially orchestrated Lewis acid activation, halogen-atom transfer, radical addition, single-electron reduction and β-fluoro elimination has been developed.     

The Morita–Baylis–Hillman reaction for non-electron-deficient olefins enabled by photoredox catalysis

A strategy for overcoming the limitation of the Morita–Baylis–Hillman (MBH) reaction, which is only applicable to electron-deficient olefins, has been achieved via visible-light induced photoredox catalysis in this report. A series of non-electron-deficient olefins underwent the MBH reaction smoothly via a novel photoredox-quinuclidine dual catalysis. The in situ formed key β-quinuclidinium radical intermediates, derived from the addition of olefins with quinuclidinium radical cations, are used to enable the MBH reaction of non-electron-deficient olefins. On the basis of previous reports, a plausible mechanism is suggested. Mechanistic studies, such as radical probe experiments and density functional theory (DFT) calculations, were also conducted to support our proposed reaction pathways.

A strategy for overcoming the limitation of the Morita–Baylis–Hillman (MBH) reaction, which is only applicable to electron-deficient olefins, has been achieved via visible-light induced photoredox catalysis in this report.     

Sensitization-initiated electron transfer via upconversion: mechanism and photocatalytic applications

Sensitization-initiated electron transfer (SenI-ET) describes a recently discovered photoredox strategy that relies on two consecutive light absorption events, triggering a sequence of energy and electron transfer steps. The cumulative energy input from two visible photons gives access to thermodynamically demanding reactions, which would be unattainable by single excitation with visible light. For this reason, SenI-ET has become a very useful strategy in synthetic photochemistry, but the mechanism has been difficult to clarify due to its complexity. We demonstrate that SenI-ET can operate via sensitized triplet–triplet annihilation upconversion, and we provide the first direct spectroscopic evidence for the catalytically active species. In our system comprised of fac-[Ir(ppy)₃] as a light absorber, 2,7-di-tert-butylpyrene as an annihilator, and N,N-dimethylaniline as a sacrificial reductant, all photochemical reaction steps proceed with remarkable rates and efficiencies, and this system is furthermore suitable for photocatalytic aryl dehalogenations, pinacol couplings and detosylation reactions. The insights presented here are relevant for the further rational development of photoredox processes based on multi-photon excitation, and they could have important implications in the greater contexts of synthetic photochemistry and solar energy conversion.

A full picture of a new multi-photon excitation mechanism relying on sTTA upconversion is provided, together with selected photocatalytic applications. All mechanistic steps are investigated and the catalytically active species is observed directly.     

Mild olefin formation via bio-inspired vitamin B12 photocatalysis

Dehydrohalogenation, or elimination of hydrogen-halide equivalents, remains one of the simplest methods for the installation of the biologically-important olefin functionality. However, this transformation often requires harsh, strongly-basic conditions, rare noble metals, or both, limiting its applicability in the synthesis of complex molecules. Nature has pursued a complementary approach in the novel vitamin B₁₂-dependent photoreceptor CarH, where photolysis of a cobalt–carbon bond leads to selective olefin formation under mild, physiologically-relevant conditions. Herein we report a light-driven B₁₂-based catalytic system that leverages this reactivity to convert alkyl electrophiles to olefins under incredibly mild conditions using only earth abundant elements. Further, this process exhibits a high level of regioselectivity, producing terminal olefins in moderate to excellent yield and exceptional selectivity. Finally, we are able to access a hitherto-unknown transformation, remote elimination, using two cobalt catalysts in tandem to produce subterminal olefins with excellent regioselectivity. Together, we show vitamin B₁₂ to be a powerful platform for developing mild olefin-forming reactions.

Terminal or subterminal olefins can be selectively formed from alkyl electrophiles via bio-inspired vitamin B₁₂ photocatalysis.     

Switchable photocatalysis for the chemodivergent benzylation of 4-cyanopyridines

We report a photocatalytic strategy for the chemodivergent radical benzylation of 4-cyanopyridines. The chemistry uses a single photoredox catalyst to generate benzyl radicals upon N–F bond activation of 2-alkyl N-fluorobenzamides. The judicious choice of different photocatalyst quenchers allowed us to select at will between mechanistically divergent processes. The two reaction manifolds, an ipso-substitution path proceeding via radical coupling and a Minisci-type addition, enabled selective access to regioisomeric C4 or C2 benzylated pyridines, respectively. Mechanistic investigations shed light on the origin of the chemoselectivity switch.

We report a photocatalytic strategy for the chemodivergent radical benzylation of 4-cyanopyridines. The chemistry uses a single photoredox catalyst to generate benzyl radicals upon N–F bond activation of 2-alkyl N-fluorobenzamides.     

Asymmetric β-arylation of cyclopropanols enabled by photoredox and nickel dual catalysis

The enantioselective functionalization and transformation of readily available cyclopropyl compounds are synthetically appealing yet challenging topics in organic synthesis. Here we report an asymmetric β-arylation of cyclopropanols with aryl bromides enabled by photoredox and nickel dual catalysis. This dual catalytic transformation features a broad substrate scope and good functional group tolerance at room temperature, providing facile access to a wide array of enantioenriched β-aryl ketones bearing a primary alcohol moiety in good yields with satisfactory enantioselectivities (39 examples, up to 83% yield and 90% ee). The synthetic value of this protocol was illustrated by the concise asymmetric construction of natural product calyxolane B analogues.

An asymmetric β-arylation of cyclopropanols with aryl bromides was enabled by enantioselective photoredox and nickel dual catalysis.     

Investigations into mechanism and origin of regioselectivity in the metallaphotoredox-catalyzed α-arylation of N-alkylbenzamides

A mechanistic study on the α-arylation of N-alkylbenzamides catalyzed by a dual nickel/photoredox system using aryl bromides is reported herein. This study elucidates the origins of site-selectivity of the transformation, which is controlled by the generation of a hydrogen atom transfer (HAT) agent by a photocatalyst and bromide ions in solution. Tetrabutylammonium bromide was identified as a crucial additive and source of a potent HAT agent, which led to increases in yields and a lowering of the stoichiometries of the aryl bromide coupling partner. NMR titration experiments and Stern–Volmer quenching studies provide evidence for complexation to and oxidation of bromide by the photocatalyst, while elementary steps involving deprotonation of the N-alkylbenzamide or 1,5-HAT were ruled out through mechanistic probes and kinetic isotope effect analysis. This study serves as a valuable tool to better understand the α-arylation of N-alkylbenzamides, and has broader implications in halide-mediated C–H functionalization reactions.

A mechanistic study of the α-arylation of N-alkylbenzamides catalyzed by a dual nickel/photoredox system using aryl bromides elucidates the origins of site-selectivity of the transformation and identifies the hydrogen atom transfer agent.     

DFT insight into asymmetric alkyl–alkyl bond formation via nickel-catalysed enantioconvergent reductive coupling of racemic electrophiles with olefins

A DFT study has been conducted to understand the asymmetric alkyl–alkyl bond formation through nickel-catalysed reductive coupling of racemic alkyl bromide with olefin in the presence of hydrosilane and K₃PO₄. The key findings of the study include: (i) under the reductive experimental conditions, the Ni(ii) precursor is easily activated/reduced to Ni(0) species which can serve as an active species to start a Ni(0)/Ni(ii) catalytic cycle. (ii) Alternatively, the reaction may proceed via a Ni(i)/Ni(ii)/Ni(iii) catalytic cycle starting with a Ni(i) species such as Ni(i)–Br. The generation of a Ni(i) active species via comproportionation of Ni(ii) and Ni(0) species is highly unlikely, because the necessary Ni(0) species is strongly stabilized by olefin. Alternatively, a cage effect enabled generation of a Ni(i) active catalyst from the Ni(ii) species involved in the Ni(0)/Ni(ii) cycle was proposed to be a viable mechanism. (iii) In both catalytic cycles, K₃PO₄ greatly facilitates the hydrosilane hydride transfer for reducing olefin to an alkyl coupling partner. The reduction proceeds by converting a Ni–Br bond to a Ni–H bond via hydrosilane hydride transfer to a Ni–alkyl bond via olefin insertion. On the basis of two catalytic cycles, the origins for enantioconvergence and enantioselectivity control were discussed.

The enantioconvergent alkyl–alkyl coupling involves two competitive catalytic cycles with nickel(0) and nickel(i) active catalysts, respectively. K₃PO₄ plays a crucial role to enable the hydride transfer from hydrosilane to nickel–bromine species.     

De novo design and synthesis of dipyridopurinone derivatives as visible-light photocatalysts in productive guanylation reactions

Described here is the de novo design and synthesis of a series of 6H-dipyrido[1,2-e:2′,1′-i]purin-6-ones (DPs) as a new class of visible-light photoredox catalysts (PCs). The synthesized DP1–5 showed their λ_Abs(max) values in 433–477 nm, excited state redox potentials in 1.15–0.69 eV and −1.41 to −1.77 eV (vs. SCE), respectively. As a representative, DP4 enables the productive guanylation of various amines, including 1°, 2°, and 3°-alkyl primary amines, secondary amines, aryl and heteroaryl amines, amino-nitrile, amino acids and peptides as well as propynylamines and α-amino esters giving diversities in biologically important guanidines and cyclic guanidines. The photocatalytic efficacy of DP4 in the guanylation overmatched commonly used Ir and Ru polypyridyl complexes, and some organic PCs. Other salient merits of this method include broad substrate scope and functional group tolerance, gram-scale synthesis, and versatile late-stage derivatizations that led to a derivative 81 exhibiting 60-fold better anticancer activity against Ramos cells with the IC₅₀ of 0.086 μM than that of clinical drug ibrutinib (5.1 μM).

A novel visible-light photocatalyst was designed and its photocatalytic efficacy in the guanylation of amines overmatched common metal-core and organic photocatalysts.     

Fe-catalyzed Fukuyama-type indole synthesis triggered by hydrogen atom transfer

Fe, Co, and Mn hydride-initiated radical olefin additions have enjoyed great success in modern synthesis, yet the extension of other hydrogen radicalophiles instead of olefins remains largely elusive. Herein, we report an efficient Fe-catalyzed intramolecular isonitrile–olefin coupling reaction delivering 3-substituted indoles, in which isonitrile was firstly applied as the hydrogen atom acceptor in the radical generation step by MHAT. The protocol features low catalyst loading, mild reaction conditions, and excellent functional group tolerance.

A mild and efficient method has been developed to synthesize 3-substituted indoles via an Fe-catalyzed radical isonitrile–olefin coupling reaction initiated by MHAT to isonitriles.     

Palladium-catalyzed difluoroalkylative carbonylation of styrenes toward difluoropentanedioates

The introduction of fluorine atoms into organic molecules is an attractive but challenging topic. In this work, an interesting palladium-catalyzed difluoroalkylative carbonylation of aryl olefins has been developed. A wide range of aryl olefins were transformed into the corresponding difluoropentanedioate compounds with good functional-group tolerance and excellent regioselectivity. Inexpensive ethyl bromodifluoroacetate acts both as a difluoroalkyl precursor and a nucleophile here. Additionally, a scale–up reaction was also performed successfully, and further transformations of the obtained product were shown as well.

An interesting palladium-catalyzed difluoroalkylative carbonylation of aryl olefins has been developed. A wide range of aryl olefins were transformed into the corresponding difluoropentanedioate compounds with good functional-group tolerance and excellent regioselectivity.     

Mechanistic study of photocatalytic CO2 reduction using a Ru(ii)–Re(i) supramolecular photocatalyst

Supramolecular photocatalysts comprising [Ru(diimine)₃]²⁺ photosensitiser and fac-[Re(diimine)(CO)₃{OC(O)OC₂H₄NR₂}] catalyst units can be used to reduce CO₂ to CO with high selectivity, durability and efficiency. In the presence of triethanolamine, the Re catalyst unit efficiently takes up CO₂ to form a carbonate ester complex, and then direct photocatalytic reduction of a low concentration of CO₂, e.g., 10% CO₂, can be achieved using this type of supramolecular photocatalyst. In this work, the mechanism of the photocatalytic reduction of CO₂ was investigated applying such a supramolecular photocatalyst, RuC2Re with a carbonate ester ligand, using time-resolved visible and infrared spectroscopies and electrochemical methods. Using time-resolved spectroscopic measurements, the kinetics of the photochemical formation processes of the one-electron-reduced species RuC2(Re)−, which is an essential intermediate in the photocatalytic reaction, were clarified in detail and its electronic structure was elucidated. These studies also showed that RuC2(Re)− is stable for 10 ms in the reaction solution. Cyclic voltammograms measured at various scan rates besides temperature and kinetic analyses of RuC2(Re)− produced by steady-state irradiation indicated that the subsequent reaction of RuC2(Re)− proceeds with an observed first-order rate constant of approximately 1.8 s⁻¹ at 298 K and is a unimolecular reaction, independent of the concentrations of both CO₂ and RuC2(Re)−.

Formation processes and reactivity of an important intermediate of photocatalytic CO₂ reduction, one-electron reduced species of a Ru(ii)–Re(i) supramolecular photocatalyst with a carbonate ester ligand, were investigated in detail.     

Synthesis of C-acyl furanosides via the cross-coupling of glycosyl esters with carboxylic acids

C-Acyl furanosides are versatile synthetic precursors to a variety of natural products, nucleoside analogues, and pharmaceutical molecules. This report addresses the unmet challenge in preparing C-acyl furanosides by developing a cross-coupling reaction between glycosyl esters and carboxylic acids. A key step is the photoredox activation of the glycosyl ester, which promotes the homolysis of the strong anomeric C–O bond through CO₂ evolution to afford glycosyl radicals. This method embraces a large scope of furanoses, pyranoses, and carboxylic acids, and is readily applicable to the synthesis of a thymidine analogue and diplobifuranylone B, as well as the late-stage modification of (+)-sclareolide. The convenient preparation of the redox active glycosyl ester from native sugars and the compatibility with common furanoses exemplifies the potential of this method in medicinal chemistry.

A cross-coupling of glycosyl esters with carboxylic acids to prepare C-acyl furanosides and pyranosides. The reaction proceeds through photoredox activation of the glycosyl ester to afford glycosyl radicals.     

Catalyst-controlled selective borocarbonylation of benzylidenecyclopropanes: regiodivergent synthesis of γ-vinylboryl ketones and β-cyclopropylboryl ketones

Regioselective catalytic multi-functionalization reactions enable the rapid synthesis of complexed products from the same precursors. In this communication, we present a method for the regiodivergent borocarbonylation of benzylidenecyclopropanes with aryl iodides. Various γ-vinylboryl ketones and β-cyclopropylboryl ketones were produced in moderate to good yields with excellent regioselectivity from the same substrates. The choice of the catalyst is key for the regioselectivity control: γ-vinylboryl ketones were produced selectively with IPrCuCl and Pd(dppp)Cl₂ as the catalytic system, while the corresponding β-cyclopropylboryl ketones were obtained in high regioselectivity with Cu(dppp)Cl, [Pd(η³-cinnamyl)Cl]₂ and xantphos as the catalytic system. Moreover, γ-vinylboryl ketones and β-cyclopropylboryl ketones were successfully transformed into several other value-added products.

A novel procedure for regiodivergent borocarbonylation of benzylidenecyclopropanes has been developed. A variety of valuable γ-vinylboryl ketones and β-cyclopropylboryl ketones can be obtained selectively in excellent yields.     

Highly selective α-aryloxyalkyl C–H functionalisation of aryl alkyl ethers

We report highly selective photocatalytic functionalisations of alkyl groups in aryl alkyl ethers with a range of electron-poor alkenes using an acridinium catalyst with a phosphate base and irradiation with visible light (456 nm or 390 nm). Experiments indicate that the reaction operates via direct single-electron oxidation of the arene substrate ArOCHRR′ to its radical cation by the excited state organic photocatalyst; this is followed by deprotonation of the ArOC–H in the radical cation to yield the radical ArOC˙RR′. This radical then attacks the electrophile to form an intermediate alkyl radical that is reduced to complete the photocatalytic cycle. The oxidation step is selective for activated arenes (ArOR) over their non-activated counterparts and the subsequent deprotonation of the methoxy group affords the α-aryloxyalkyl radical that leads to a wide range of functionalised products in good to excellent yield.

We report highly selective photocatalytic functionalisations of alkyl groups in aryl alkyl ethers with a range of electron-poor alkenes using an acridinium catalyst with a phosphate base and irradiation with visible light (456 nm or 390 nm).     

Photocatalytic CO2 reduction sensitized by a special-pair mimic porphyrin connected with a rhenium(i) tricarbonyl complex

Zn porphyrins with an imidazolyl group at the meso position generate a highly stable porphyrin dimer by complementary coordination from the imidazolyl to the Zn ion in noncoordinating solvents such as chloroform, which mimics the natural special pair in photosynthesis. In this work, we have synthesized an imidazolyl-substituted Zn porphyrin connected with a Re 2,2-bipyridine tricarbonyl complex as a CO₂ reduction catalyst via a p-phenylene linker, affording a homodimer with two Re complexes on both sides (ReDRe). The dimeric structure is easily dissociated into the corresponding monomers in coordinating solvents. Therefore, we prepared a mixture containing a heterodimer with the Re carbonyl complex on one side (ReD) by simple mixing with an imidazolyl Zn porphyrin and evaporating the solvent. Using the Grubbs catalyst, the subsequent olefin metathesis reaction of the mixture gave covalently linked porphyrin dimers through the allyloxy side chains, enabling the isolation of the stable hetero- (ReD′) and homo-dimers (ReD′Re) with gel permeation chromatography. The Zn porphyrin dimers have intense absorption bands in the visible light region and acted as good photosensitizers in photocatalytic CO₂ reduction in a mixture of N,N-dimethylacetamide and triethanolamine (5 : 1 v/v) containing 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole as the electron donor, giving CO with high selectivity and durability. Under irradiation with strong light intensity, the reaction rate in ReD′ exceeded that of the previous porphyrin Re complex dyad, ZnP-phen=Re. For instance, after irradiation at 560 nm for 18 h, the turnover number (TON_CO) of ReD′ reached 2800, whereas the TON_CO of ZnP-phen=Re was 170. The high activity in the system using the porphyrin dimer originates from no accumulation of the one-electron reduced species of the porphyrin that inhibit light absorption due to the inner-filter effect.

An artificial special pair was connected with a Re 2,2-bipyridine tricarbonyl complex. The special pair derivative acted as a good photosensitizer in photocatalytic CO₂ reduction, giving CO with high selectivity and durability.     

Design of well-defined shell–core covalent organic frameworks/metal sulfide as an efficient Z-scheme heterojunction for photocatalytic water splitting

Development of a covalent–organic framework (COF)-based Z-scheme heterostructure is a promising strategy for solar energy driven water splitting, but the construction of a COF-based Z-scheme heterostructure with well-defined architecture, large contact area and intimate contact interfaces is scarce. Herein, we fabricated a direct Z-scheme heterostructure COF–metal sulfide hybrid (T-COF@CdS) with shell–core architecture by self-polymerization of 1,3,5-benzenetricarboxaldehyde and 2,4,6-tris(4-aminophenyl)-1,3,5-triazine in situ on CdS. The formed C–S chemical bonding between T-COF and CdS could provide a very tight and stable interface. Owing to the properly staggered band alignment, strong interfacial interaction and large interfacial contact area between T-COF and CdS, a Z-scheme route for charge separation and transfer is realized, resulting in electron accumulation in CdS for H₂O reduction. The obtained Z-scheme heterostructure T-COF@CdS-3 exhibits a high apparent quantum efficiency of 37.8% under 365 nm monochromatic light irradiation, and long-term stability arising from shell–core structures in which the T-COF shell protects the catalytic centers of CdS against deactivation, as well as acts as oxidation sites to avoid the photocorrosion of CdS. This work provides a strategy for the construction of a shell–core direct Z-scheme heterostructure photocatalyst for water splitting with high performance.

A stable Z-scheme with well-defined architecture by in situ growth of COFs on CdS for photocatalytic water splitting is constructed. The T-COF shell can protect the catalytic center of CdS from deactivation and photocorrosion.     

Asymmetric [3 + 2] photocycloadditions of cyclopropylamines with electron-rich and electron-neutral olefins

Radical addition to olefins is a common and useful chemical transformation. In the context of offering enantioenriched three-dimensional molecules via such a highly reactive process, chiral hydrogen-bonding (H-bonding) catalysis has been widely used to provide enantiocontrol. The current strategies for operating H-bonding induction are confined to following that are prevalent in ionic-type manifolds. Here, we report a novel protocol towards electron-rich olefins based on converting these species from acting as H-bonding donors to acceptors. It facilitates the first development of asymmetric [3 + 2] photocycloadditions with cyclopropylamines. The method is also effective for electron-neutral olefins, in which the successful construction of all-carbon quaternary stereocentres from 1,1-diaryl ethylenes that feature two structurally similar aryl substituents demonstrates the versatility of this new chiral H-bonding catalytic strategy. Furthermore, the importance of the obtained six kinds of products in pharmaceuticals and asymmetric catalysis underscores the practicability of this work.

Radical addition to olefins is a common and useful chemical transformation.     

Diastereoselective and enantioselective photoredox pinacol coupling promoted by titanium complexes with a red-absorbing organic dye

The pinacol coupling reaction, a reductive coupling of carbonyl compounds that proceeds through the formation of ketyl radicals in the presence of an electron donor, affords the corresponding 1,2-diols in one single step. The photoredox version of this transformation has been accomplished using different organic dyes or photoactive metal complexes in the presence of sacrificial donors such as tertiary amines or Hantzsch''s ester. Normally, the homo-coupling of such reactive ketyl radicals is neither diastereo- nor enantio-selective. Herein, we report a highly diastereoselective pinacol coupling reaction of aromatic aldehydes promoted by 5 mol% of the non-toxic, inexpensive and available Cp₂TiCl₂ complex. The key feature that allows the complete control of diastereoselectivity is the employment of a red-absorbing organic dye in the presence of a redox-active titanium complex. Taking advantage of the well-tailored photoredox potential of this organic dye, the selective reduction of Ti(iv) to Ti(iii) is achieved. These conditions enable the formation of the d,l (syn) diastereoisomer as the favored product of the pinacol coupling (d.r. > 20 : 1 in most of the cases). Moreover, employing a simply prepared chiral SalenTi complex, the new photoredox reaction gave a complete diastereoselection for the d,l diastereoisomer, and high enantiocontrol (up to 92% of enantiomeric excess).

A metallaphotoredox, diastereoselective and enantioselective pinacol coupling reaction promoted by titanium complexes with the use of a red-absorbing organic dye was developed.     

Homogeneous molecular catalysis of the electrochemical reduction of N2O to N2: redox vs. chemical catalysis

Homogeneous electrochemical catalysis of N₂O reduction to N₂ is investigated with a series of organic catalysts and rhenium and manganese bipyridyl carbonyl complexes. An activation-driving force correlation is revealed with the organic species characteristic of a redox catalysis involving an outer-sphere electron transfer from the radical anions or dianions of the reduced catalyst to N₂O. Taking into account the previously estimated reorganization energy required to form the N₂O radical anions leads to an estimation of the N₂O/N₂O˙⁻ standard potential in acetonitrile electrolyte. The direct reduction of N₂O at a glassy carbon electrode follows the same quadratic activation driving force relationship. Our analysis reveals that the catalytic effect of the mediators is due to a smaller reorganization energy of the homogeneous electron transfer than that of the heterogeneous one. The physical effect of “spreading” electrons in the electrolyte is shown to be unfavorable for the homogeneous reduction. Importantly, we show that the reduction of N₂O by low valent rhenium and manganese bipyridyl carbonyl complexes is of a chemical nature, with an initial one-electron reduction process associated with a chemical reaction more efficient than the simple outer-sphere electron transfer process. This points to an inner-sphere mechanism possibly involving partial charge transfer from the low valent metal to the binding N₂O and emphasizes the differences between chemical and redox catalytic processes.

Homogeneous electrochemical catalysis of N₂O reduction to N₂ is investigated with a series of organic catalysts and rhenium and manganese bipyridyl carbonyl complexes.