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Themed collection Metal-Mediated Transformations of Small Molecules

16 articles
Editorial

Metal-mediated transformations of small molecules

Guest editors Louise A. Berben and Jason B. Love introduce this web collection showcasing outstanding contributions in the field of the design, development, and exploitation of metal mediated transformations of small molecules.

Graphical abstract: Metal-mediated transformations of small molecules
Feature Article

Nitrogenase: a general hydrogenator of small molecules

Nitrogenase naturally converts N2 to NH3, and also hydrogenates a variety of small molecules. A unified mechanistic theory for these additions of multiple hydrogen atoms to small molecules is outlined, together with proposed testing experiments.

Graphical abstract: Nitrogenase: a general hydrogenator of small molecules
Open Access Communication

Five-coordinate MII-semiquinonate (M = Fe, Mn, Co) complexes: reactivity models of the catechol dioxygenases

The first mononuclear iron(II)-semiquinonate has been prepared. Analogous manganese and cobalt adducts are reported, including a cobalt(II)-semiquinonate that exhibits O2-mediated intradiol oxidation.

Graphical abstract: Five-coordinate MII-semiquinonate (M = Fe, Mn, Co) complexes: reactivity models of the catechol dioxygenases
Communication

Solvent and electrolyte effects on Ni(PR2NR′2)2-catalyzed electrochemical oxidation of hydrogen

We report solvent and electrolyte effects on the electrocatalytic oxidation of H2 using Ni(PCy2NR′2)2 (R′ = Bn, tBu) complexes.

Graphical abstract: Solvent and electrolyte effects on Ni(PR2NR′2)2-catalyzed electrochemical oxidation of hydrogen
Communication

Dioxygen activation by an organometallic Pd(II) precursor: formation of a Pd(IV)–OH complex and its C–O bond formation reactivity

An isolable Pd(IV)–OH complex formed upon aerobic oxidation of an organometallic Pd(II) precursor exhibits selective C(sp2)–O bond formation reactivity.

Graphical abstract: Dioxygen activation by an organometallic Pd(ii) precursor: formation of a Pd(iv)–OH complex and its C–O bond formation reactivity
Communication

Peroxynitrite chemistry derived from nitric oxide reaction with a Cu(II)–OOH species and a copper mediated NO reductive coupling reaction

New peroxynitrite–copper chemistry ensues via addition of ˙NO(g) to a CuII–hydroperoxo species; the ligand–Cu(I) complex was shown to effect ˙NO(g) reductive coupling.

Graphical abstract: Peroxynitrite chemistry derived from nitric oxide reaction with a Cu(ii)–OOH species and a copper mediated NO reductive coupling reaction
Communication

Reductive deoxygenation of CO2 by a bimetallic titanium bis(pentalene) complex

The bimetallic bis(pentalene) complex Ti2(μ:η55-C8H4{SiiPr3-1,4}2)2 reduces CO2 to afford dicarbonyl and bridging oxo-complexes.

Graphical abstract: Reductive deoxygenation of CO2 by a bimetallic titanium bis(pentalene) complex
Open Access Communication

Binding and activation of small molecules by a quintuply bonded chromium dimer

A Cr–Cr quintuple bond undergoes [2+n] cycloadditions to generate dimetallacycles retaining Cr–Cr quadruple bonds.

Graphical abstract: Binding and activation of small molecules by a quintuply bonded chromium dimer
Communication

Synthesis, structure and reactivity of FeII/III–NH3 complexes bearing a tripodal sulfonamido ligand

Complexes [MnMST(NH3)]n−3 (Mn = FeII, FeIII, GaIII) were prepared and each contains a intramolecular hydrogen bonding network involving the ammonia ligand.

Graphical abstract: Synthesis, structure and reactivity of FeII/III–NH3 complexes bearing a tripodal sulfonamido ligand
Communication

pH dependence of the electroreduction of nitrate on Rh and Pt polycrystalline electrodes

From a study of the electrocatalytic reduction of nitrate on Pt and Rh electrodes over a wide pH range, HNO3 is suggested as the only reducible species in nitrate reduction on Pt, whereas both HNO3 and the nitrate anion are reducible on Rh.

Graphical abstract: pH dependence of the electroreduction of nitrate on Rh and Pt polycrystalline electrodes
Communication

Activation of gaseous PH3 with low coordinate diaryltetrylene compounds

Two modes of reactivity are observed when pyrophoric phosphine gas reacts with diaryltetrylenes, representing unique main-group P–H bond activation.

Graphical abstract: Activation of gaseous PH3 with low coordinate diaryltetrylene compounds
Communication

Reactivity of a fac-ReCl(α-diimine)(CO)3 complex with an NAD+ model ligand toward CO2 reduction

A rhenium complex containing an NADH-like model ligand has been prepared and used for electrochemical CO2 reduction.

Graphical abstract: Reactivity of a fac-ReCl(α-diimine)(CO)3 complex with an NAD+ model ligand toward CO2 reduction
Communication

Making syngas electrocatalytically using a polypyridyl ruthenium catalyst

In acetonitrile solutions saturated in CO2 with added water and weak acid, the polypyridyl complex [Ru(tpy)(bpy)(NCCH3)]2+ acts as an electrocatalyst for the formation of syngas mixtures of H2 and CO.

Graphical abstract: Making syngas electrocatalytically using a polypyridyl ruthenium catalyst
Communication

Synthesis of titanium and zirconium complexes supported by a p-terphenoxide ligand and their reactions with N2, CO2 and CS2

The low-valent chemistry of titanium and zirconium complexes supported by a p-terphenoxide ligand is described, leading to μ-N2, geminal diolate and ethylenetetrathiolate derivatives and arene C–H activation.

Graphical abstract: Synthesis of titanium and zirconium complexes supported by a p-terphenoxide ligand and their reactions with N2, CO2 and CS2
Open Access Communication

Preparation and reactivity of a dinitrogen-bridged dimolybdenum-tetrachloride complex

A dinitrogen-bridged dimolybdenum-tetrachloride complex is prepared and reduced with Super-Hydride (LiBHEt3) to afford the corresponding dimolybdenum-dinitrogen complex together with the formation of molecular dihydrogen. This reaction proceeds via the ligand exchange of the coordinated dihydrogen generated in situ with molecular dinitrogen.

Graphical abstract: Preparation and reactivity of a dinitrogen-bridged dimolybdenum-tetrachloride complex
Open Access Communication

Preparation and reactivity of molybdenum–dinitrogen complexes bearing an arsenic-containing ANA-type pincer ligand

Molybdenum–dinitrogen complexes bearing an arsenic-containing ANA-type pincer ligand are prepared. These complexes afford ammonia by treatment with sulfuric acid at room temperature.

Graphical abstract: Preparation and reactivity of molybdenum–dinitrogen complexes bearing an arsenic-containing ANA-type pincer ligand
16 articles

About this collection

The themed collection includes contributions from molecular inorganic chemists, biological chemists, electrochemists, and theoreticians who are working toward understanding and developing productive transformations of small molecules: dinitrogen, carbon dioxide, carbon monoxide, dihydrogen and dioxygen. Contributions will describe the activation of these molecules and, in particular, metal-mediated transformations of these small molecules such as reduction, oxidation, and bond forming and breaking events. This issue is Guest Edited by Louise A. Berben and Jason Love. New articles will be added to this collection as they are published.

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