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.
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.
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.
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.
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.
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.
Reductive deoxygenation of CO2 by a bimetallic titanium bis(pentalene) complex
The bimetallic bis(pentalene) complex Ti2(μ:η5,η5-C8H4{SiiPr3-1,4}2)2 reduces CO2 to afford dicarbonyl and bridging oxo-complexes.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.