Characterization of reactive organometallic species via MicroED

Here we apply microcrystal electron diffraction (MicroED) to the structural determination of transition metal complexes. We find that the simultaneous use of 300 keV electrons, very low electron doses, and an ultra-sensitive camera allows for the collection of data without cryogenic cooling of the stage. This technique reveals the first crystal structures of the classic zirconocene hydride, colloquially known as “Schwartz’s reagent”, a novel Pd(II) complex not amenable to solution-state NMR or X-ray crystallography, and five other paramagnetic or diamagnetic transition metal complexes.

Characterization of reactive organometallic species via MicroED

Here we apply microcrystal electron diffraction (MicroED) to the structural determination of transition metal complexes. We find that the simultaneous use of 300 keV electrons, very low electron doses, and an ultra-sensitive camera allows for the collection of data without cryogenic cooling of the stage. This technique reveals the first crystal structures of the classic zirconocene hydride, colloquially known as “Schwartz’s reagent”, a novel Pd(II) complex not amenable to solution-state NMR or X-ray crystallography, and five other paramagnetic or diamagnetic transition metal complexes.

Characterization of reactive organometallic species via MicroED

Here we apply microcrystal electron diffraction (MicroED) to the structural determination of transition metal complexes. We find that the simultaneous use of 300 keV electrons, very low electron doses, and an ultra-sensitive camera allows for the collection of data without cryogenic cooling of the stage. This technique reveals the first crystal structures of the classic zirconocene hydride, colloquially known as “Schwartz’s reagent”, a novel Pd(II) complex not amenable to solution-state NMR or X-ray crystallography, and five other paramagnetic or diamagnetic transition metal complexes.

Structural and Superconducting Properties of Thermal Treatment-Synthesised Bulk YBa2Cu3O7−δ Superconductor: Effect of Addition of SnO2 Nanoparticles

YBa2Cu3O7−δ (Y-123) bulk superconductors with the addition of (0.0, 0.2, 0.4, 0.6, 0.8, and 1.0 wt.%) SnO2 nanoparticles were synthesised via a thermal treatment method. The influence of SnO2 addition on the superconducting properties by means of critical temperature, Tc, AC susceptibility, phase formation and microstructures, including its elemental composition analysis, were studied. Sharp superconducting transition, ∆Tc, and diamagnetic transition were obtained for all SnO2-added samples. It was observed that sample x = 0.4 with a Y-123 phase percentage of 95.8% gives the highest Tc, smallest ∆Tc, and the sharpest diamagnetic transition in the normalised susceptibility curves. The microstructure also showed an excess of Sn precipitates on the sample’s surface at x = 0.8 and above. As such, the best superconducting properties were observed at x = 0.4 SnO2 addition inside the Y-123 host sample.

H2 Binding, Splitting, and Net Hydrogen Atom Transfer at a Paramagnetic Iron Complex

<div>The reactivity of H2 with abundant transition metals is crucial for developing catalysts for energy storage in chemical bonds. While diamagnetic transition metal complexes that bind and split H2 have been extensively studied, paramagnetic complexes that exhibit this behavior remain rare. We describe the reactivity of a square planar S = ½ FeI(P4N2)+ cation (FeI+) that reversibly binds H2/D2 in solution, exhibiting an inverse equilibrium isotope effect of KH2/KD2 = 0.58(4) at -5.0 °C. In the presence of excess H2, the dihydrogen complex FeI(H2)+ cleaves H2 at 25 °C in a net hydrogen atom transfer reaction to give the dihydrogen-hydride cation trans-FeII(H)(H2)+. The proposed mechanism of H2 splitting involves both intra- and intermolecular steps, resulting in a mixed firstand second-order rate law with respect to initial [FeI+]. The key intermediate is a paramagnetic dihydride complex, trans-FeIII(H)2+, whose weak FeIII-H bond dissociation free energy (calculated BDFE = 44 kcal/mol) leads to bimetallic H-H homolysis, generating trans-FeII(H)(H2)+. Reaction kinetics, thermodynamics, electrochemistry, EPR spectroscopy, and DFT calculations all support the</div><div>proposed reaction mechanism.</div>

H2 Binding, Splitting, and Net Hydrogen Atom Transfer at a Paramagnetic Iron Complex

<div>The reactivity of H2 with abundant transition metals is crucial for developing catalysts for energy storage in chemical bonds. While diamagnetic transition metal complexes that bind and split H2 have been extensively studied, paramagnetic complexes that exhibit this behavior remain rare. We describe the reactivity of a square planar S = ½ FeI(P4N2)+ cation (FeI+) that reversibly binds H2/D2 in solution, exhibiting an inverse equilibrium isotope effect of KH2/KD2 = 0.58(4) at -5.0 °C. In the presence of excess H2, the dihydrogen complex FeI(H2)+ cleaves H2 at 25 °C in a net hydrogen atom transfer reaction to give the dihydrogen-hydride cation trans-FeII(H)(H2)+. The proposed mechanism of H2 splitting involves both intra- and intermolecular steps, resulting in a mixed firstand second-order rate law with respect to initial [FeI+]. The key intermediate is a paramagnetic dihydride complex, trans-FeIII(H)2+, whose weak FeIII-H bond dissociation free energy (calculated BDFE = 44 kcal/mol) leads to bimetallic H-H homolysis, generating trans-FeII(H)(H2)+. Reaction kinetics, thermodynamics, electrochemistry, EPR spectroscopy, and DFT calculations all support the</div><div>proposed reaction mechanism.</div>