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A bis(pyridyl)amine-bipyridine-iron(II) framework (Fe(BPAbipy)) of complexes 1-3 is reported to shed light on the multistep nature of CO2 reduction. Herein, photocatalytic conversion of CO2 to CO even at low CO2 concentration (1 %), together with detailed mechanistic study and DFT calculations, reveal that 1 first undergoes two sequential one-electron transfer affording an intermediate with electron density on both Fe and ligand for CO2 binding over proton. The following 2 H+ -assisted Fe-CO formation is rate-determining for selective CO2 -to-CO reduction. A pendant, proton-shuttling α-OH group (2) initiates PCET for predominant H2 evolution, while an α-OMe group (3) cancels the selectivity control for either CO or H2 . The near-unity selectivity of 1 and 2 enables self-sorting syngas production at flexible CO/H2 ratios. The unprecedented results from one kind of molecular catalyst skeleton encourage insight into the beauty of advanced multi-electron and multi-proton transfer processes for robust CO2 RR by photocatalysis.

Described herein is an IrIII /porphyrin-catalyzed intermolecular C(sp3 )-H insertion reaction of a quinoid carbene (QC). The reaction was designed by harnessing the hydrogen-atom transfer (HAT) reactivity of a metal-QC species with aliphatic substrates followed by a radical rebound process to afford C-H arylation products. This methodology is efficient for the arylation of activated hydrocarbons such as 1,4-cyclohexadienes (down to 40 min reaction time, up to 99 % yield, up to 1.0 g scale). It features unique regioselectivity, which is mainly governed by steric effects, as the insertion into primary C-H bonds is favored over secondary and/or tertiary C-H bonds in the substituted cyclohexene substrates. Mechanistic studies revealed a radical mechanism for the reaction.

We report the isolation, X-ray crystal structures, reactivity and DFT calculations of iron- and ruthenium-mono(dialkylcarbene) and osmium-bis(dialkylcarbene) porphyrins and diarylcarbene transfer/insertion reactions catalyzed by iron-mono(dialkylcarbene) porphyrin., Alkyl-substituted carbene (CHR or CR2, R = alkyl) complexes have been extensively studied for alkylcarbene (CHR) ligands coordinated with high-valent early transition metal ions (a.k.a. Schrock carbenes or alkylidenes), yet dialkylcarbene (CR2) complexes remain less developed with bis(dialkylcarbene) species being little (if at all) explored. Herein, several group 8 metal porphyrin dialkylcarbene complexes, including Fe- and Ru-mono(dialkylcarbene) complexes [M(Por)(Ad)] (1a,b, M = Fe, Por = porphyrinato dianion, Ad = 2-adamantylidene; 2a,b, M = Ru) and Os-bis(dialkylcarbene) complexes [Os(Por)(Ad)2] (3a–c), are synthesized and crystallographically characterized. Detailed investigations into their electronic structures reveal that these complexes are formally low-valent M(ii)-carbene in nature. These complexes display remarkable thermal stability and chemical inertness, which are rationalized by a synergistic effect of strong metal-carbene covalency, hyperconjugation, and a rigid diamondoid carbene skeleton. Various spectroscopic techniques and DFT calculations suggest that the dialkylcarbene Ad ligand is unique compared to other common carbene ligands as it acts as both a potent σ-donor and π-acceptor; its unique electronic and structural features, together with the steric effect of the porphyrin macrocycle, make its Fe porphyrin complex 1a an active and robust catalyst for intermolecular diarylcarbene transfer reactions including cyclopropanation (up to 90% yield) and X–H (X = S, N, O, C) insertion (up to 99% yield) reactions.

Direct C-H bond functionalization catalyzed by non-precious transition metals is an attractive strategy in synthetic chemistry. Compared with the precious metals rhodium, palladium, ruthenium, and iridium commonly used in this field, catalysis based on non-precious metals, especially the earth-abundant ones, is appealing due to the increasing demand for environmentally benign and sustainable chemical processes. Herein, developments in iron- and cobalt-catalyzed C(sp3)-H bond functionalization reactions are described, with an emphasis on their applications in organic synthesis, i.e., the synthesis of natural products and pharmaceuticals and/or their modification.

Visible light driven nitrene transfer and insertion reactions of organic azides are an attractive strategy for the design of C–N bond formation reactions under mild reaction conditions, the challenge being lack of selectivity as a free nitrene reactive intermediate is usually involved. Herein is described an iron(iii) porphyrin catalysed sp3 C–H amination and alkene aziridination with selectivity by using organic azides as the nitrogen source under blue LED light (469 nm) irradiation. The photochemical reactions display chemo- and regio-selectivity and are effective for the late-stage functionalization of natural and bioactive compounds with complexity. Mechanistic studies revealed that iron porphyrin plays a dual role as a photosensitizer and as a catalyst giving rise to a reactive iron–nitrene intermediate for subsequent C–N bond formation., An iron(iii) porphyrin catalysed sp3 C–H amination and alkene aziridination with broad substrate scope under mild conditions is conducted, with selectivity through the use of organic azides as the nitrogen source under blue LED light irradiation.

High-valent iron-nitrido species are nitrogen analogues of iron-oxo species which are versatile reagents for C-H oxidation. Nonetheless, C-H activation by iron-nitrido species has been scarcely explored, as this is often hampered by their instability and short lifetime in solutions. Herein, the hydrogen atom transfer (HAT) reactivity of an Fe porphyrin nitrido species (2 c) toward C-H substrates was studied in solutions at room temperature, which was achieved by nanosecond laser flash photolysis (LFP) of its FeIII -azido precursor (1 c) supported by a bulky bis-pocket porphyrin ligand. C-H bonds with bond dissociation enthalpies (BDEs) of up to ≈84 kcal mol-1 could be activated, and the second-order rate constants (k2 ) are on the order of 102 -104 s-1 m-1 . The Fe-amido product formed after HAT could further release ammonia upon protonation.

Reliable methods for enantioselective cis-dihydroxylation of trisubstituted alkenes are scarce. The iron(II) complex cis-α-[FeII (2-Me2 -BQPN)(OTf)2 ], which bears a tetradentate N4 ligand (Me2 -BQPN=(R,R)-N,N'-dimethyl-N,N'-bis(2-methylquinolin-8-yl)-1,2-diphenylethane-1,2-diamine), was prepared and characterized. With this complex as the catalyst, a broad range of trisubstituted electron-deficient alkenes were efficiently oxidized to chiral cis-diols in yields of up to 98 % and up to 99.9 % ee when using hydrogen peroxide (H2 O2 ) as oxidant under mild conditions. Experimental studies (including 18 O-labeling, ESI-MS, NMR, EPR, and UV/Vis analyses) and DFT calculations were performed to gain mechanistic insight, which suggested possible involvement of a chiral cis-FeV (O)2 reaction intermediate as an active oxidant. This cis-[FeII (chiral N4 ligand)]2+ /H2 O2 method could be a viable green alternative/complement to the existing OsO4 -based methods for asymmetric alkene dihydroxylation reactions.

Cobalt(II)-porphyrin catalyzed intramolecular Buchner reaction and arene cyclopropanation of alkyl diazomethanes in situ generated from N-tosylhydrazones to give a range of bicyclic cycloheptatriene fused pyrrolidines and tetracyclic cyclopropane fused pyrrolidines in good to high yields and with high chemo- and regio-selectivity. The obtained cyclopropane fused pyrrolidines can be readily converted to other N-heterocycles with potential synthetic and biological interests.

Reactivity study of novel metal carbene complexes can offer new opportunities in catalytic carbene transfer reactions as well as in other synthetic protocols. Metal complexes with quinoid carbene (QC) ligands are assumed to be key intermediates in a variety of metal-catalyzed QC transfer reactions using diazo quinones, which demands development of the chemistry of QC transfer of well characterized metal-QC complexes. Herein we report the isolation and QC transfer of ruthenium porphyrins [Ru(Por)(QC)] which contribute the first examples of (i) structurally characterized metal-QC complex (by X-ray crystallography) and (ii) isolated metal-QC complex that undergoes QC transfer reaction. The complexes [Ru(Por)(QC)] were prepared from reaction of [Ru(Por)(CO)] with diazo quinones and exhibited dual reactivity, i.e., hydrogen atom transfer (HAT) as well as QC transfer. The stoichiometric QC transfer reactions from these Ru-QC complexes to nitrosoarenes (ArNO) afforded nitrones in up to 90% yield, and the corresponding catalytic reactions were also developed. Both the stoichiometric and catalytic reactions for a series of QC ligands bearing electron-donating and -withdrawing substituents showed a reverse substituent effect on the QC transfer reactivity. Complexes [Ru(Por)(QC)] are also reactive toward C-H and X-H (X = N, S) bonds and can catalyze aerobic oxidation of 1,4-cyclohexadiene; their stoichiometric HAT reactions with unsaturated hydrocarbons gave product yields of up to 88%. The unique dual reactivity and electronic feature of [Ru(Por)(QC)] were studied by spectroscopic means and density functional theory (DFT) calculations.

Correction for ‘Stable group 8 metal porphyrin mono- and bis(dialkylcarbene) complexes: synthesis, characterization, and catalytic activity’ by Hai-Xu Wang et al., Chem. Sci., 2020, 11, 2243–2259, DOI: 10.1039/C9SC05432D.