Bioinspired metal complexes for energy-related photocatalytic small molecule transformation
Bridging and axial carbene binding modes in cobalt corrole complexes: effect on carbene transfer
Two different types of carbene intermediates are observed in the reaction of ethyl diazoacetate (EDA) with different Co corrole complexes, and their properties and reactivities are reported.
Ambiphilicity of a mononuclear cobalt(III) superoxo complex
Addition of HOTf to a mixture of CoIII(BDPP)(O2˙) (1) and Cp*2Fe produced H2O2 in high yield implying formation of CoIII(BDPP)(OOH) (3), and reaction of Sc(OTf)3 with the same mixture gave a peroxo-bridged CoIII/ScIII5.
Catalytic O2 activation with synthetic models of α-ketoglutarate dependent oxygenases
An iron complex with a tridentate 1,4,7-triazacyclononane ligand mimics structural and functional features of α-ketoglutarate (α-KG) dependent enzymes, and engages in catalytic O2 activation coupled to α-KG decarboxylation and sulfide oxygenation.
Revisiting amorphous molybdenum sulfide's activity for the electro-driven reduction of dinitrogen and N-containing substrates
Amorphous molybdenum sulfide exhibits partial nitrogenase-like activity allowing for the electro driven reduction of azides under aqueous conditions.
Mobility of Lewis acids within the secondary coordination sphere: toward a model for cooperative substrate binding
Distance dependence of appended Lewis acids in N2H4 binding and deprotonation was evaluated within a series of zinc complexes.
Ligand regulation for manganese-catalyzed enantioselective epoxidation of olefins without acid
A manganese-catalyzed asymmetric epoxidation of olefins is developed under acid-free conditions. MnIVO species serves as an active species.
Kinetic and mechanistic analysis of a synthetic reversible CO2/HCO2− electrocatalyst
A kinetic and mechanistic analysis of [Pt(depe)2](PF6)2, an electrocatalyst for the reversible conversion between CO2 and HCO2− with high selectivity at low overpotentials.
Copper arylnitrene intermediates: formation, structure and reactivity
The mechanism of oxidation of arylamines by copper enzymes is not clarified yet. A possible pathway involves copper(II)oxyl intermediates transforming arylamines to copper aryl nitrenes. We investigate details of this pathway in a gas phase reaction.
Spin-resolved charge displacement analysis as an intuitive tool for the evaluation of cPCET and HAT scenarios
The spin-resolved version of the charge displacement function is introduced as an intuitive tool for differentiating between hydrogen-atom transfer and concerted proton-coupled electron transfer.
Synthesis of a B12–BODIPY dyad for B12-inspired photochemical transformations of a trichloromethylated organic compound
A B12 complex–BODIPY dyad was synthesized by peripheral modification of cobalamin derivatives.
A NiRhS fuel cell catalyst – lessons from hydrogenase
Novel dry-distilled catalysts based on Rh, Ni and S were developed via a Ni(μ-S)2Rh organometallic [NiFe]hydrogenase mimic.
A heterogeneous bio-inspired peroxide shunt for catalytic oxidation of organic molecules
Iron porphyrins with three different axial ligands installed atop self-assembled monolayer modified gold electrodes can oxidize C–H bonds and epoxidize alkenes efficiently using H2O2via the formation of a high-valent intermediate.
Proton-promoted disproportionation of iron(V)-imido TAML to iron(V)-imido TAML cation radical and iron(IV) TAML
An iron(V)-imido TAML complex is disproportionated to give an iron(V)-imido TAML cation radical and an iron(IV) TAML upon addition of acids.
Bimetallic iron–tin catalyst for N2 to NH3 and a silyldiazenido model intermediate
A new tin-supported iron complex catalyzes N2 fixation. The role of this heavy main group element in the catalysis is evaluated.
Selective catalytic 2e−-oxidation of organic substrates by an FeII complex having an N-heterocyclic carbene ligand in water
An FeII complex, 1, having a pentadentate ligand with an NHC moiety catalyzes substrate oxidation to afford 2e−-oxidized products with high selectivity by suppression of overoxidation in water.
Controlled O2 reduction at a mixed-valent (II,I) Cu2S core
Oxygen reduction reactions catalyzed by a mixed-valent copper complex reveal a tuneable H2O2/H2O selectivity at room temperature together with high stability over several cycles.
Nucleophilic reactivity of a mononuclear cobalt(III)–bis(tert-butylperoxo) complex
A mononuclear cobalt(III)–bis(tert-butylperoxo) adduct (CoIII–(OOtBu)2) bearing a tetraazamacrocyclic ligand was synthesized and characterized using various physicochemical methods, such as X-ray, UV-vis, ESI-MS, EPR, and NMR analyses.
Metal–ligand cooperativity across two sites of a square planar iron(II) complex ligated by a tetradentate PNNP ligand
A square planar (PNNP)FeII complex is shown to readily activate two B–H bonds across the Fe–amide linkages in an overall four-electron process facilitated by metal–ligand cooperativity.
A dinuclear Mo2H8 complex supported by bulky C5H2tBu3 ligands
A simple dinuclear hydride complex consisting of only Mo, hydrides, and cyclopentadienyl ligands was synthesized and tested for benzene activation.
Preparation and reactivity of molybdenum complexes bearing pyrrole-based PNP-type pincer ligand
Molybdenum complexes bearing an anionic pyrrole-based PNP-type pincer ligand have been prepared and have been found to work as catalysts for the conversion of N2 into NH3 under ambient conditions.