Reversible H_2 Addition across a Nickel−Borane Unit as a Promising Strategy for Catalysis

We report the synthesis and characterization of a series of nickel complexes of the chelating diphosphine-borane ligands ArB(o-Ph_2PC_6H_4)_2 ([^(Ar)DPB^(Ph)]; Ar = Ph, Mes). The [^(Ar)DPB^(Ph)] framework supports pseudo-tetrahedral nickel complexes featuring η^2-B,C coordination from the ligand backbone. For the B-phenyl derivative, the THF adduct [^(Ph)DPB^(Ph)]Ni(THF) has been characterized by X-ray diffraction and features a very short interaction between nickel and the η^2-B,C ligand. For the B-mesityl derivative, the reduced nickel complex [^(Mes)DPB^(Ph)]Ni is isolated as a pseudo-three-coordinate “naked” species that undergoes reversible, nearly thermoneutral oxidative addition of dihydrogen to give a borohydrido-hydride complex of nickel(II) which has been characterized in solution by multinuclear NMR. Furthermore, [^(Mes)DPB^(Ph)]Ni is an efficient catalyst for the hydrogenation of olefin substrates under mild conditions

CO2 reduction with protons and electrons at a boron-based reaction center.

Borohydrides are widely used reducing agents in chemical synthesis and have emerging energy applications as hydrogen storage materials and reagents for the reduction of CO2. Unfortunately, the high energy cost associated with the multistep preparation of borohydrides starting from alkali metals precludes large scale implementation of these latter uses. One potential solution to this issue is the direct synthesis of borohydrides from the protonation of reduced boron compounds. We herein report reactions of the redox series [Au(B2P2)] n (n = +1, 0, -1) (B2P2, 9,10-bis(2-(diisopropylphosphino)phenyl)-9,10-dihydroboranthrene) and their conversion into corresponding mono- and diborohydride complexes. Crucially, the monoborohydride can be accessed via protonation of [Au(B2P2)]-, a masked borane dianion equivalent accessible at relatively mild potentials (-2.05 V vs. Fc/Fc+). This species reduces CO2 to produce the corresponding formate complex. Cleavage of the formate complex can be achieved by reduction (ca. -1.7 V vs. Fc/Fc+) or by the addition of electrophiles including H+. Additionally, direct reaction of [Au(B2P2)]- with CO2 results in reductive disproportion to release CO and generate a carbonate complex. Together, these reactions constitute a synthetic cycle for CO2 reduction at a boron-based reaction center that proceeds through a B-H unit generated via protonation of a reduced borane with weak organic acids

A Limited Habitable Zone for Complex Life

The habitable zone (HZ) is commonly defined as the range of distances from a host star within which liquid water, a key requirement for life, may exist on a planet's surface. Substantially more CO2 than present in Earth's modern atmosphere is required to maintain clement temperatures for most of the HZ, with several bars required at the outer edge. However, most complex aerobic life on Earth is limited by CO2 concentrations of just fractions of a bar. At the same time, most exoplanets in the traditional HZ reside in proximity to M dwarfs, which are more numerous than Sun-like G dwarfs but are predicted to promote greater abundances of gases that can be toxic in the atmospheres of orbiting planets, such as carbon monoxide (CO). Here we show that the HZ for complex aerobic life is likely limited relative to that for microbial life. We use a 1D radiative-convective climate and photochemical models to circumscribe a Habitable Zone for Complex Life (HZCL) based on known toxicity limits for a range of organisms as a proof of concept. We find that for CO2 tolerances of 0.01, 0.1, and 1 bar, the HZCL is only 21%, 32%, and 50% as wide as the conventional HZ for a Sun-like star, and that CO concentrations may limit some complex life throughout the entire HZ of the coolest M dwarfs. These results cast new light on the likely distribution of complex life in the universe and have important ramifications for the search for exoplanet biosignatures and technosignatures.Comment: Revised including additional discussion. Published Gold OA in ApJ. 9 pages, 5 figures, 5 table

Thing Theory

This article is an extended review of Graham Harman's Heidegger Explained: From Phenomenon to Thing. The paper explains Harman's argument that Heidegger's famous broken tool incident - the account that introduces a critique of presence based on the withdrawn dimensions of things - has a much greater relevance than is usually imagined. It explores Harman's extrapolations from Heidegger to rethink the very nature of objects - or things in themselves, their relations to each other, and their own unfathomable inner being. The paper goes on to note the implications of this argument for thinking more generally about relationality, space, and the more-than-human

Abiotic O2_{2} Levels on Planets around F, G, K, and M Stars: Possible False Positives for Life?

In the search for life on Earth-like planets around other stars, the first (and likely only) information will come from the spectroscopic characterization of the planet's atmosphere. Of the countless number of chemical species terrestrial life produces, only a few have the distinct spectral features and the necessary atmospheric abundance to be detectable. The easiest of these species to observe in Earth's atmosphere is O$_{2}$ (and its photochemical byproduct, O$_{3}$). But O$_{2}$ can also be produced abiotically by photolysis of CO$_{2}$, followed by recombination of O atoms with each other. CO is produced in stoichiometric proportions. Whether O$_{2}$ and CO can accumulate to appreciable concentrations depends on the ratio of far-UV to near-UV radiation coming from the planet's parent star and on what happens to these gases when they dissolve in a planet's oceans. Using a one-dimensional photochemical model, we demonstrate that O$_{2}$ derived from CO$_{2}$ photolysis should not accumulate to measurable concentrations on planets around F- and G-type stars. K-star, and especially M-star planets, however, may build up O$_{2}$ because of the low near-UV flux from their parent stars, in agreement with some previous studies. On such planets, a 'false positive' for life is possible if recombination of dissolved CO and O$_{2}$ in the oceans is slow and if other O$_{2}$ sinks (e.g., reduced volcanic gases or dissolved ferrous iron) are small. O$_{3}$, on the other hand, could be detectable at UV wavelengths ($\lambda$ < 300 nm) for a much broader range of boundary conditions and stellar types.Comment: 20 pages text, 9 figure

The Ursinus Weekly, March 23, 1906

A phase of nature • A reverie • Exhibition of the work of the Biological Department • Alumni • Zwinglian anniversary • Society notes • Pennsylvania relay races • Dr. Shaw\u27s lecture • YMCA officers • Personals • Special lecturehttps://digitalcommons.ursinus.edu/weekly/2974/thumbnail.jp

Nuclear-resonant electron scattering

We investigate nuclear-resonant electron scattering as occurring in the two-step process of nuclear excitation by electron capture (NEEC) followed by internal conversion. The nuclear excitation and decay are treated by a phenomenological collective model in which nuclear states and transition probabilities are described by experimental parameters. We present capture rates and resonant strengths for a number of heavy ion collision systems considering various scenarios for the resonant electron scattering process. The results show that for certain cases resonant electron scattering can have significantly larger resonance strengths than NEEC followed by the radiative decay of the nucleus. We discuss the impact of our findings on the possible experimental observation of NEEC.Comment: 24 pages, 2 plots, 5 table