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Herein is reported the structural characterization and scalable preparation of the elusive iron–phosphido complex FpP( t Bu)(F) (2-F, Fp = (Fe(η 5 -C 5 H 5 )(CO) 2 )) and its precursor FpP( t Bu)(Cl) (2-Cl) in 51% and 71% yields, respectively. These phosphide complexes are proposed to be relevant to an organoiron catalytic cycle for phosphinidene transfer to electron-deficient alkenes. Examination of their properties led to the discovery of a more efficient catalytic system involving the simple, commercially available organoiron catalyst Fp 2 . This improved catalysis also enabled the preparation of new phosphiranes with high yields ( t BuPCH 2 CHR; R = CO 2 Me, 41%; R = CN, 83%; R = 4-biphenyl, 73%; R = SO 2 Ph, 71%; R = POPh 2 , 70%; R = 4-pyridyl, 82%; R = 2-pyridyl, 67%; R = PPh 3 + , 64%) and good diastereoselectivity, demonstrating the feasibility of the phosphinidene group-transfer strategy in synthetic chemistry. Experimental and theoretical studies suggest that the original catalysis involves 2-X as the nucleophile, while for the new Fp 2 -catalyzed reaction they implicate a diiron–phosphido complex Fp 2 (P t Bu), 4, as the nucleophile which attacks the electron-deficient olefin in the key first P–C bond-forming step. In both systems, the initial nucleophilic attack may be accompanied by favorable five-membered ring formation involving a carbonyl ligand, a (reversible) pathway competitive with formation of the three-membered ring found in the phosphirane product. A novel radical mechanism is suggested for the new Fp 2 -catalyzed system. 

Abstract The Ediacaran Period (~635–539 Ma) is marked by the emergence and diversification of complex metazoans linked to ocean redox changes, but the processes and mechanism of the redox evolution in the Ediacaran ocean are intensely debated. Here we use mercury isotope compositions from multiple black shale sections of the Doushantuo Formation in South China to reconstruct Ediacaran oceanic redox conditions. Mercury isotopes show compelling evidence for recurrent and spatially dynamic photic zone euxinia (PZE) on the continental margin of South China during time intervals coincident with previously identified ocean oxygenation events. We suggest that PZE was driven by increased availability of sulfate and nutrients from a transiently oxygenated ocean, but PZE may have also initiated negative feedbacks that inhibited oxygen production by promoting anoxygenic photosynthesis and limiting the habitable space for eukaryotes, hence abating the long-term rise of oxygen and restricting the Ediacaran expansion of macroscopic oxygen-demanding animals. 

In the last few decades, the development of nontraditional isotope (e.g., Mo, Tl, U) measurements of redox sensitive metals provided information about the redox evolution of Earth’s oceans and atmosphere. Rhenium (Re) isotopes have the potential to fill a critical gap in the isotope proxy toolkit. Currently, there are proxies for ocean-basin-scale oxygenated and anoxic (0 uM O2 with no H2S) conditions, but there is not yet a proxy that can detect when large parts of the oceans were in a low-O2 but not anoxic condition, termed ‘suboxic’ (10 ≥ O2 > 0 uM). Detecting suboxic conditions is particularly important because some aerobic organisms can live in extremely low-O2 waters (down to ~10 nM O2; Stolper et al. 2010), and so it is of great interest to know when large parts of the ocean crossed from anoxic to suboxic conditions. Rhenium concentrations have been used as a paleoredox proxy to track suboxic and anoxic marine redox conditions locally, but do not easily extend globally. Because of the long residence time of Re in the oceans, the Re isotope proxy can likely track changes in the extent of suboxic conditions globally in the ocean. Previous publications provided methods for digesting and purifying Re for δ187Re analysis from different materials (e.g., seawater, basalt, sedimentary rocks, chondrites; Miller et al., 2015, Liu et al., 2017, Dellinger et al., 2019, Dickson et al., 2020). These publications set the foundation for creating a δ187Re ocean mass balance. However, there is as yet no method that specifically targets the authigenic Re in shales, which has the potential to directly capture δ187Re of contemporaneous seawater. Here, we report a novel method for digesting samples that is done in a single step that excludes the use of HF, utilizing the well-established Carius tube (CT) digestion technique. By not using HF, this method does not dissolve the silicate portion of samples, allowing the targeted removal of authigenic Re. We also introduce a two-step column chemistry approach that can be utilized to purify Re from large samples with very low Re concentrations. We are applying this new method to characterize δ187Re in modern euxinic and suboxic settings including the Black Sea and the Benguela margin. 

Abstract The driving forces, kill and recovery mechanisms for the end-Permian mass extinction (EPME), the largest Phanerozoic biological crisis, are under debate. Sedimentary records of mercury enrichment and mercury isotopes have suggested the impact of volcanism on the EPME, yet the causes of mercury enrichment and isotope variations remain controversial. Here, we model mercury isotope variations across the EPME to quantitatively assess the effects of volcanism, terrestrial erosion and photic zone euxinia (PZE, toxic, sulfide-rich conditions). Our numerical model shows that while large-scale volcanism remains the main driver of widespread mercury enrichment, the negative shifts of Δ¹⁹⁹Hg isotope signature across the EPME cannot be fully explained by volcanism or terrestrial erosion as proposed before, but require additional fractionation by marine mercury photoreduction under enhanced PZE conditions. Thus our model provides further evidence for widespread and prolonged PZE as a key kill mechanism for both the EPME and the impeded recovery afterward. 

Tactile information is detected by thermoreceptors and mechanoreceptors in the skin and integrated by the central nervous system to produce the perception of somatosensation. Here we investigate the mechanism by which thermal and mechanical stimuli begin to interact and report that it is achieved by the mechanotransduction apparatus in cutaneous mechanoreceptors. We show that moderate cold potentiates the conversion of mechanical force into excitatory current in all types of mechanoreceptors from mice and tactile-specialist birds. This effect is observed at the level of mechanosensitive Piezo2 channels and can be replicated in heterologous systems using Piezo2 orthologs from different species. The cold sensitivity of Piezo2 is dependent on its blade domains, which render the channel resistant to cold-induced perturbations of the physical properties of the plasma membrane and give rise to a different mechanism of mechanical activation than that of Piezo1. Our data reveal that Piezo2 is an evolutionarily conserved mediator of thermal–tactile integration in cutaneous mechanoreceptors.