Themed collection Bioinspired metal complexes for chemical transformations and catalysis

Overview of the rich and diverse contributions of quantum chemistry to understanding the structure and function of the biological archetypes for solar fuel research, photosystem II and hydrogenases.

This article features the recent progress of bioinspired metal complexes as catalysts with high stability, specific selectivity and satisfactory efficiency to drive multiple-electron and multiple-proton related to small molecule transformation.

Using inspiration from biological cofactors, the reversible storage of hydrogen on a supporting dihydrazonopyrrole ligand enables catalytic hydrogenation reactivity with nickel.

DFT calculations reveal that halogen bonds and 3c-4e bonds make a difference in the metal-iodylarene chemistry.

A mononuclear oxoiron(IV) complex 1-trans bearing two equatorial sulfur ligations is synthesized and characterized as an active-site model of the elusive sulfur-ligated Fe^IVO intermediates in non-heme iron oxygenases.

Multiple H₂O₂-forming mechanisms are accessible in Fe(porphyrin)-catalysed oxygen reduction, a key reaction in both fuel cell technologies and oxygen-utilizing enzymes.

Modulating alkene reactivity from oxygenation to halogenation with an exogenous ligand via O₂ electrochemical reductive activation.

A semi-empirical approach allows determining the His axial-ligand orientation with respect to the porphyrin plane in synthetic heme-peroxidases, for structure/function analysis.

Even though β-diketiminato nickel(II) bromide and cobaltocene have nearly identical redox potentials the corresponding electron transfer complex can be crystallised from the equilibrium and activates CO₂ to form a mononuclear nickel(II) carbonate.

A guide for the spectroscopic differentiation of iron complexes with square-pyramidal, conjugated, pyridinic environments is presented.

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.

Addition of HOTf to a mixture of Co^III(BDPP)(O₂˙) (1) and Cp*₂Fe produced H₂O₂ in high yield implying formation of Co^III(BDPP)(OOH) (3), and reaction of Sc(OTf)₃ with the same mixture gave a peroxo-bridged Co^III/Sc^III5.

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.

Amorphous molybdenum sulfide exhibits partial nitrogenase-like activity allowing for the electro driven reduction of azides under aqueous conditions.

Distance dependence of appended Lewis acids in N₂H₄ binding and deprotonation was evaluated within a series of zinc complexes.

A manganese-catalyzed asymmetric epoxidation of olefins is developed under acid-free conditions. Mn^IVO species serves as an active species.

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.

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.

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.

A B₁₂ complex–BODIPY dyad was synthesized by peripheral modification of cobalamin derivatives.

Novel dry-distilled catalysts based on Rh, Ni and S were developed via a Ni(μ-S)₂Rh organometallic [NiFe]hydrogenase mimic.

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.

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.

A new tin-supported iron complex catalyzes N₂ fixation. The role of this heavy main group element in the catalysis is evaluated.

An Fe^II 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.

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.

A mononuclear cobalt(III)–bis(tert-butylperoxo) adduct (Co^III–(OO^tBu)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.

A square planar (PNNP)Fe^II 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 simple dinuclear hydride complex consisting of only Mo, hydrides, and cyclopentadienyl ligands was synthesized and tested for benzene activation.

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.