Synthetic pentlandite (FeNiS) is a promising electrocatalyst for hydrogen evolution, demonstrating high current densities, low overpotential, and remarkable stability in bulk form. The depletion of sulfur from the surface of this catalyst during the electrochemical reaction has been proposed to be beneficial for its catalytic performance, but the role of sulfur vacancies and the mechanism determining the reaction kinetics are still unknown. We have performed electrochemical operando studies of the vibrational dynamics of pentlandite under hydrogen evolution reaction conditions using Fe nuclear resonant inelastic X-ray scattering. Comparing the measured Fe partial vibrational density of states with density functional theory calculations, we have demonstrated that hydrogen atoms preferentially occupy substitutional positions replacing pre-existing sulfur vacancies. Once all vacancies are filled, the protonation proceeds interstitially, which slows down the reaction. Our results highlight the beneficial role of sulfur vacancies in the electrocatalytic performance of pentlandite and give insights into the hydrogen adsorption mechanism during the reaction.

A new family of benzoresorufin-based copper complexes for fluorescence detection of NO and HNO is reported. The copper complexes, CuBRNO1-3, elicit 1.5-4.8-fold emission enhancement in response to NO and HNO. The three sensors differ in the nature of the metal-binding site. The photophysical properties of these sensors are investigated with assistance from density functional theory calculations. The fluorescence turn-on observed upon reaction with HNO is an unexpected result that is discussed in detail. The utility of the new sensors for detecting HNO and NO in HeLa cells and RAW 264.7 macrophages is demonstrated.

A new, DMF-coordinated, pre-organized diiron compound [Fe2(N-Et-HPTB)(DMF)4](BF4)3 (1) was synthesized, avoiding the formation of [Fe(N-Et-HPTB)](BF4)2 (10) and [Fe2(N-Et-HPTB)(μ-MeCONH)](BF4)2 (11), where N-Et-HPTB is the anion of N,N,N’,N’-tetrakis(2-(1-ethylbenzimidazolyl))-2-hydroxy-1,3-diaminopropane. Compound 1 is a versatile reactant from which nine new compounds have been generated. Transformations include solvent exchange to yield [Fe2(N-Et-HPTB)(MeCN)4](BF4)3 (2), substitution to afford [Fe2(N-Et-HPTB)(μ-RCOO)](BF4)2 (3, R = Ph; 4, RCOO = 4-methyl-2,6-diphenyl benzoate]), one-electron oxidation by (Cp2Fe)(BF4) to yield a Robin-Day class II mixed valent diiron(II,III) compound, [Fe2(N-Et-HPTB)(μ-PhCOO)(DMF)2](BF4)3 (5), two-electron oxidation with tris(4-bromophenyl)aminium hexachloroantimonate to generate [Fe2(N-Et-HPTB)Cl3(DMF)](BF4)2 (6), reaction with TEMPO (2,2,6,6-tetramethylpiperidin-1-yl)oxyl) to form [Fe5(N-Et-HPTB)2(μ-OH)4(μ-O)(DMF)2](BF4)4 (7), and reaction with dioxygen to yield an unstable peroxo compound that decomposes at room temperature to generate [Fe4(N-Et-HPTB)2(μ-O)3(H2O)2](BF4)·8DMF (8) and [Fe4(N-Et-HPTB)2(μ-O)4](BF4)2 (9). Compound 5 loses its bridging benzoate ligand upon further oxidation to form [Fe2(N-Et-HPTB)(OH)2(DMF)2](BF4)3 (12). Reaction of the diiron(II,III) compound (5) with dioxygen was studied in detail by spectroscopic methods. All compounds (1-12) were characterized by single crystal X-ray structure determinations. Selected compounds and reaction intermediates were further examined by a combination of elemental analysis, electronic absorption spectroscopy, Mössbauer spectroscopy, EPR spectroscopy, resonance Raman spectroscopy, and cyclic voltammetry.

(Bis‐selenolato) and (bis‐tellurolato)diiron complexes [2Fe2E(Si)] were prepared and compared with the known (bis‐thiolato)diiron complex A to assess their ability to produce hydrogen from protons. Treatment of [Fe3(CO)12] with 4,4‐dimethyl‐1,2,4‐diselenasilolane (1) in boiling toluene afforded hexacarbonyl{μ‐{[1,1′‐(dimethylsilylene)bis[methaneselenolato‐κSe : κSe]](2 −)}}diiron(FeFe) (2). The analog bis‐tellurolato complex hexacarbonyl{μ‐{[1,1′‐(dimethylsilylene)bis[methanetellurolato‐κTe : κTe]](2 −)}}diiron(FeFe) (3) was obtained by treatment of [Fe3(CO)12] with dimethylbis(tellurocyanatomethyl)dimethylsilane, which was prepared in situ. All compounds were characterized by NMR, IR spectroscopy, mass spectrometry, elemental analysis and single‐crystal X‐ray analysis. The electrocatalytic properties of the [2Fe2X(Si)] (X=S, Se, Te) model complexes A, 1, and 2 towards hydrogen formation were evaluated.