Preparation, Structure, and Reactivity of Nonstabilized Organoiron Compounds. Implications for Iron-Catalyzed Cross Coupling Reactions

A series of unprecedented organoiron complexes of the formal oxidation states −2, 0, +1, +2, and +3 is presented, which are largely devoid of stabilizing ligands and, in part, also electronically unsaturated (14-, 16-, 17- and 18-electron counts). Specifically, it is shown that nucleophiles unable to undergo β-hydride elimination, such as MeLi, PhLi, or PhMgBr, rapidly reduce Fe(3+) to Fe(2+) and then exhaustively alkylate the metal center. The resulting homoleptic organoferrate complexes [(Me4Fe)(MeLi)][Li(OEt2)]2 (3) and [Ph4Fe][Li(Et2O)2][Li(1,4-dioxane)] (5) could be characterized by X-ray crystal structure analysis. However, these exceptionally sensitive compounds turned out to be only moderately nucleophilic, transferring their organic ligands to activated electrophiles only, while being unable to alkylate (hetero)aryl halides unless they are very electron deficient. In striking contrast, Grignard reagents bearing alkyl residues amenable to β-hydride elimination reduce FeXn (n = 2, 3) to clusters of the formal composition [Fe(MgX)2]n. The behavior of these intermetallic species can be emulated by structurally well-defined lithium ferrate complexes of the type [Fe(C2H4)4][Li(tmeda)]2 (8), [Fe(cod)2][Li(dme)]2 (9), [CpFe(C2H4)2][Li(tmeda)] (7), [CpFe(cod)][Li(dme)] (11), or [Cp*Fe(C2H4)2][Li(tmeda)] (14). Such electron-rich complexes, which are distinguished by short intermetallic Fe−Li bonds, were shown to react with aryl chlorides and allyl halides; the structures and reactivity patterns of the resulting organoiron compounds provide first insights into the elementary steps of low valent iron-catalyzed cross coupling reactions of aryl, alkyl, allyl, benzyl, and propargyl halides with organomagnesium reagents. However, the acquired data suggest that such C−C bond formations can occur, a priori, along different catalytic cycles shuttling between metal centers of the formal oxidation states Fe(+1)/Fe(+3), Fe(0)/Fe(+2), and Fe(−2)/Fe(0). Since these different manifolds are likely interconnected, an unambiguous decision as to which redox cycle dominates in solution remains difficult, even though iron complexes of the lowest accessible formal oxidation states promote the reactions most effectively

Synthetic 26Al emission from galactic-scale superbubble simulations

© 2019 The Author(s).Emission from the radioactive trace element 26Al has been observed throughout the Milky Way with the COMPTEL and INTEGRAL satellites. In particular the Doppler shifts measured with INTEGRAL connect 26Al with superbubbles, which may guide 26Al flows off spiral arms in the direction of Galactic rotation. In order to test this paradigm, we have performed galaxy-scale simulations of superbubbles with 26Al injection in a Milky Way-type galaxy. We produce all-sky synthetic $\gamma-$ray emission maps of the simulated galaxies. We find that the 1809keV emission from the radioactive decay of 26Al is highly variable with time and the observer's position. This allows us to estimate an additional systematic variability of 0.2dex for a star formation rate derived from 26Al for different times and measurement locations in Milky Way-type galaxies. High-latitude morphological features indicate nearby emission with correspondingly high integrated gamma-ray intensities. We demonstrate that the 26Al scale height from our simulated galaxies depends on the assumed halo gas density. We present the first synthetic 1809keV longitude-velocity diagrams from 3D hydrodynamic simulations. The line-of-sight velocities for 26Al can be significantly different from the line-of-sight velocities associated with the cold gas. Over time, 26Al velocities consistent with the INTEGRAL observations, within uncertainties, appear at any given longitude, broadly supporting previous suggestions that 26Al injected into expanding superbubbles by massive stars may be responsible for the high velocities found in the INTEGRAL observations. We discuss the effect of systematically varying the location of the superbubbles relative to the spiral arms.Peer reviewedFinal Accepted Versio

Dynamics and Energy Loss in Superbubbles

Martin G. H. Krause, and Roland Diehl, “Dynamics and Energy Loss in Superbubble”, The Astrophysical Journal Letters, Vol. 794(2), October 2014. © 2014. The American Astronomical Society. All rights reserved. Printed in the U.S.A.Interstellar bubbles appear to be smaller in observations than expected from calculations. Instabilities at the shell boundaries create three-dimensional (3D) effects and are probably responsible for part of this discrepancy. We investigate instabilities and dynamics in superbubbles using 3D hydrodynamics simulations with time-resolved energy input from massive stars, including supernova explosions. We find that the superbubble shells are accelerated by supernova explosions, coincident with substantial brightening in soft X-ray emission. In between the explosions, the superbubbles lose energy efficiently, approaching the momentum-conserving snowplow limit. This and enhanced radiative losses due to instabilities reduce the expansion compared to the corresponding radiative bubbles in pressure-driven snowplow models with constant energy input. We note generally good agreement with observations of superbubbles and some open issues. In particular, there are hints that the shell velocities in the X-ray-bright phases are underpredicted.Peer reviewe

Energetics of positron states trapped at vacancies in solids

We report a computational first-principles study of positron trapping at vacancy defects in metals and semiconductors. The main emphasis is on the energetics of the trapping process including the interplay between the positron state and the defect's ionic structure and on the ensuing annihilation characteristics of the trapped state. For vacancies in covalent semiconductors the ion relaxation is a crucial part of the positron trapping process enabling the localization of the positron state. However, positron trapping does not strongly affect the characteristic features of the electronic structure, e.g., the ionization levels change only moderately. Also in the case of metal vacancies the positron-induced ion relaxation has a noticeable effect on the calculated positron lifetime and momentum distribution of annihilating electron-positron pairs.Comment: Submitted to Physical Review B on 17 April 2007. Revised version submitted on 6 July 200

Constraining New Forces in the Casimir Regime Using the Isoelectronic Technique

We report the first isoelectronic differential force measurements between a Au-coated probe and two Au-coated films, made out of Au and Ge. These measurements, performed at submicron separations using soft microelectromechanical torsional oscillators, eliminate the need for a detailed understanding of the probe-film Casimir interaction. The observed differential signal is directly converted into limits on the parameters $\alpha$ and $\lambda$ which characterize Yukawa-like deviations from Newtonian gravity. We find \alpha \lsim 10^{12} for $\lambda \sim 200$ nm, an improvement of $\sim$ 10 over previous limits.Comment: 10 pages, 4 figure

Kinematic and Thermal Structure at the onset of high-mass star formation

We want to understand the kinematic and thermal properties of young massive gas clumps prior to and at the earliest evolutionary stages of high-mass star formation. Do we find signatures of gravitational collapse? Do we find temperature gradients in the vicinity or absence of infrared emission sources? Do we find coherent velocity structures toward the center of the dense and cold gas clumps? To determine kinematics and gas temperatures, we used ammonia, because it is known to be a good tracer and thermometer of dense gas. We observed the NH$_3$(1,1) and (2,2) lines within seven very young high-mass star-forming regions with the VLA and the Effelsberg 100m telescope. This allows us to study velocity structures, linewidths, and gas temperatures at high spatial resolution of 3-5$"$, corresponding to $\sim$0.05 pc. We find on average cold gas clumps with temperatures in the range between 10 K and 30 K. The observations do not reveal a clear correlation between infrared emission peaks and ammonia temperature peaks. We report an upper limit for the linewidth of $\sim$1.3 km s$^{-1}$, at the spectral resolution limit of our VLA observation. This indicates a relatively low level of turbulence on the scale of the observations. Velocity gradients are present in almost all regions with typical velocity differences of 1 to 2 km s$^{-1}$ and gradients of 5 to 10 km s$^{-1}$ pc$^{-1}$. These velocity gradients are smooth in most cases, but there is one exceptional source (ISOSS23053), for which we find several velocity components with a steep velocity gradient toward the clump centers that is larger than 30 km s$^{-1}$ pc$^{-1}$. This steep velocity gradient is consistent with recent models of cloud collapse. Furthermore, we report a spatial correlation of ammonia and cold dust, but we also find decreasing ammonia emission close to infrared emission sources.Comment: 20 pages, 10 figure

Fragmentation and dynamical collapse of the starless high-mass star-forming region IRDC18310-4

Aims: We study the fragmentation and dynamical properties of a massive starless gas clump at the onset of high-mass star formation. Methods: Based on Herschel continuum data we identify a massive gas clump that remains far-infrared dark up to 100mum wavelengths. The fragmentation and dynamical properties are investigated by means of Plateau de Bure Interferometer and Nobeyama 45m single-dish spectral line and continuum observations. Results: The massive gas reservoir fragments at spatial scales of ~18000AU in four cores. Comparing the spatial extent of this high-mass region with intermediate- to low-mass starless cores from the literature, we find that linear sizes do not vary significantly over the whole mass regime. However, the high-mass regions squeeze much more gas into these similar volumes and hence have orders of magnitude larger densities. The fragmentation properties of the presented low-to high-mass regions are consistent with gravitational instable Jeans fragmentation. Furthermore, we find multiple velocity components associated with the resolved cores. Recent radiative transfer hydrodynamic simulations of the dynamic collapse of massive gas clumps also result in multiple velocity components along the line of sight because of the clumpy structure of the regions. This result is supported by a ratio between viral and total gas mass for the whole region <1. Conclusions: This apparently still starless high-mass gas clump exhibits clear signatures of early fragmentation and dynamic collapse prior to the formation of an embedded heating source. A comparison with regions of lower mass reveals that the linear size of star-forming regions does not necessarily have to vary much for different masses, however, the mass reservoirs and gas densities are orders of magnitude enhanced for high-mass regions compared to their lower-mass siblings.Comment: 11 pages, 10 figures, accepted to Astronomy and Astrophysics, high-resolution version with all figures included can be found at http://www.mpia.de/homes/beuther/papers.htm

Liquorproteine bei der Neuromyelitis optica

Es werden zwei Fälle von Neuromyelitis optica beschrieben, die jeweils eine hochgradige Erhöhung der Proteine im Liquor aufwiesen. Während ein Patient nach 6monatigem Krankheitsverlauf starb und pathologisch-anatomisch untersucht werden konnte, überlebte der andere Patient mit erheblichen Residuen. Dieser Fall zeichnete sich dadurch aus, daß deutlich erhöhte IgA- und IgM-Werte sowohl im Liquor als auch im Serum vorlagen. Es wird diskutiert, ob die gefundenen Liquorveränderungen möglicherweise eine Abgrenzung entsprechender Fälle gegenüber der multiplen Sklerose zulassen

The Changing Financial Structure of the U.S. Farm Sector

Agricultural Finance,