SOMOphilic Alkynylation of Unreactive Alkenes Enabled by Iron-Catalyzed Hydrogen Atom Transfer

We report an efficient and practical iron-catalyzed hydrogen atom transfer protocol for assembling acetylenic motifs into functional alkenes. Diversities of internal alkynes could be obtained from readily available alkenes and acetylenic sulfones with excellent Markovnikov selectivity. An iron hydride hydrogen atom transfer catalytic cycle was described to clarify the mechanism of this reaction.

Examining the emission and transmission spectra of WASP-79b with retrieval

<p>Retrieval tools provide a way of determining an exoplanet atmosphere's temperature structure and composition with an observed planetary spectrum, working backwards to determine the chemistry and temperature by iteratively comparing synthetic spectra that have been constructed via a forward model to the observed spectra and determining a best-fit result (Barstow and Heng, 2020). This talk will be presenting the emission and reanalysed transmission spectrum and retrieval analysis of WASP-79b, an inflated hot Jupiter first detected by Smalley et al. (2012). Previous transmission spectra of WASP-79b has been analysed in Sozten et al. (2020), Skaf et al. (2020), and Rathcke et al. (2021); all studies agreeing on detections of H2O with various confidence levels, with the latter finding moderate evidence of an H- bound-free opacity compared to iron hydride abundance found by the other studies. Using the publicly available \verb+Iraclis+ data analysis pipeline and the Bayesian atmospheric retrieval framework TauREx 3, we will be adding to the global picture of this planet by examining the Hubble Space Telescope emission spectra as captured by the Wide Field Camera 3 G141 grism (PI: David Sing, proposal ID: 14767). </p>

Behavior of light elements in iron-silicate-water-sulfur system during early Earth’s evolution

Hydrogen (H) is considered to be one of the candidates for light elements in the Earth’s core, but the amount and timing of delivery have been unknown. We investigated the effects of sulfur (S), another candidate element in the core, on deuteration of iron (Fe) in iron–silicate–water system up to 6–12 GPa, ~ 1200 K using in situ neutron diffraction measurements. The sample initially contained saturated water (D2O) as Mg(OD)2 in the ideal composition (Fe–MgSiO3–D2O) of the primitive Earth. In the existence of water and sulfur, phase transitions of Fe, dehydration of Mg(OD)2, and formation of iron sulfide (FeS) and silicates occurred with increasing temperature. The deuterium (D) solubility (x) in iron deuterides (FeDx) increased with temperature and pressure, resulting in a maximum of x = 0.33(4) for the hydrous sample without S at 11.2 GPa and 1067 K. FeS was hardly deuterated until Fe deuteration had completed. The lower D concentrations in the S-containing system do not exceed the miscibility gap (x < ~ 0.4). Both H and S can be incorporated into solid Fe and other light elements could have dissolved into molten iron hydride and/or FeS during the later process of Earth’s evolution.

Hydrogen evolution, electron-transfer, hydride-transfer reactions in a nickel-iron hydrogenase model complex: A theoretical study of the distinctive reactivities for the conformational isomers of nickel-iron hydride

Hydrogen fuel is a promising alternative to fossil fuel. Therefore, efficient hydrogen production is crucial to elucidate the distinctive reactivities of metal hydride species, the intermediates formed during hydrogen activation/evolution...