A multi-iron system capable of rapid N\u3csub\u3e2\u3c/sub\u3e formation and N \u3csub\u3e2\u3c/sub\u3e cleavage

The six-electron oxidation of two nitrides to N2 is a key step of ammonia synthesis and decomposition reactions on surfaces. In molecular complexes, nitride coupling has been observed with terminal nitrides, but not with bridging nitride complexes that more closely resemble catalytically important surface species. Further, nitride coupling has not been reported in systems where the nitrides are derived from N2. Here, we show that a molecular diiron(II) diiron(III) bis(nitride) complex reacts with Lewis bases, leading to the rapid six-electron oxidation of two bridging nitrides to form N2. Surprisingly, these mild reagents generate high yields of iron(I) products from the iron(II/III) starting material. This is the first molecular system that both breaks and forms the triple bond of N2 at room temperature. These results highlight the ability of multi-iron species to decrease the energy barriers associated with the activation of strong bonds. © 2014 American Chemical Society

Clinical Management of a Patient With Pure Word Deafness

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Long-term survival characteristics in stroke induced aphasia

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Binding of dinitrogen to an iron-sulfur-carbon site

© 2015 Macmillan Publishers Limited. All rights reserved. Nitrogenases are the enzymes by which certain microorganisms convert atmospheric dinitrogen (N2) to ammonia, thereby providing essential nitrogen atoms for higher organisms. The most common nitrogenases reduce atmospheric N2 at the FeMo cofactor, a sulfur-rich iron-molybdenum cluster (FeMoco). The central iron sites that are coordinated to sulfur and carbon atoms in FeMoco have been proposed to be the substrate binding sites, on the basis of kinetic and spectroscopic studies. In the resting state, the central iron sites each have bonds to three sulfur atoms and one carbon atom. Addition of electrons to the resting state causes the FeMoco to react with N2, but the geometry and bonding environment of N2 -bound species remain unknown. Here we describe a synthetic complex with a sulfur-rich coordination sphere that, upon reduction, breaks an Fe-S bond and binds N2. The product is the first synthetic Fe-N2 complex in which iron has bonds to sulfur and carbon atoms, providing a model for N2 coordination in the FeMoco. Our results demonstrate that breaking an Fe-S bond is a chemically reasonable route to N2 binding in the FeMoco, and show structural and spectroscopic details for weakened N2 on a sulfur-rich iron site

Bis(η5-penta­methyl­cyclo­penta­dien­yl)cobalt(II)

The crystal structure of the title compound, deca­methyl­cobaltocene, [Co(C10H15)2], has been determined. High-quality single crystals were grown from a cold saturated hexa­methyl­disiloxane solution. The structure is related to the manganese and iron analogs. The molecule has D 5d symmetry, with the Co atom in a crystallographic 2/m position. The cobalt–centroid(C5) distance is 1.71Å and the centroid(C5)–Co–centroid(C5) angle is 180°, by symmetry

Spectra and Light Curves of Failed Supernovae

Astronomers have proposed a number of mechanisms to produce supernova explosions. Although many of these mechanisms are now not considered primary engines behind supernovae, they do produce transients that will be observed by upcoming ground-based surveys and NASA satellites. Here we present the first radiation-hydrodynamics calculations of the spectra and light curves from three of these "failed" supernovae: supernovae with considerable fallback, accretion induced collapse of white dwarfs, and energetic helium flashes (also known as type .Ia supernovae).Comment: 33 pages, 14 figure

El tercer sector es posa al dia amb la creació d'aplicacions mòbils socials

A series of mononuclear nickel­(II) thiolate complexes (Et₄N)­Ni­(X-pyS)₃ (Et₄N = tetraethylammonium; X = 5-H (<b>1a</b>), 5-Cl (<b>1b</b>), 5-CF₃ (<b>1c</b>), 6-CH₃ (<b>1d</b>); pyS = pyridine-2-thiolate), Ni­(pySH)₄(NO₃)₂ (<b>2</b>), (Et₄N)­Ni­(4,6-Y₂-pymS)₃ (Y = H (<b>3a</b>), CH₃ (<b>3b</b>); pymS = pyrimidine-2-thiolate), and Ni­(4,4′-Z-2,2′-bpy)­(pyS)₂ (Z = H (<b>4a</b>), CH₃ (<b>4b</b>), OCH₃ (<b>4c</b>); bpy = bipyridine) have been synthesized in high yield and characterized. X-ray diffraction studies show that <b>2</b> is square planar, while the other complexes possess tris-chelated distorted-octahedral geometries. All of the complexes are active catalysts for both the photocatalytic and electrocatalytic production of hydrogen in 1/1 EtOH/H₂O. When coupled with fluorescein (Fl) as the photosensitizer (PS) and triethylamine (TEA) as the sacrificial electron donor, these complexes exhibit activity for light-driven hydrogen generation that correlates with ligand electron donor ability. Complex <b>4c</b> achieves over 7300 turnovers of H₂ in 30 h, which is among the highest reported for a molecular noble metal-free system. The initial photochemical step is reductive quenching of Fl* by TEA because of the latter’s greater concentration. When system concentrations are modified so that oxidative quenching of Fl* by catalyst becomes more dominant, system durability increases, with a system lifetime of over 60 h. System variations and cyclic voltammetry experiments are consistent with a CECE mechanism that is common to electrocatalytic and photocatalytic hydrogen production. This mechanism involves initial protonation of the catalyst followed by reduction and then additional protonation and reduction steps to give a key Ni–H^–/N–H⁺ intermediate that forms the H–H bond in the turnover-limiting step of the catalytic cycle. A key to the activity of these catalysts is the reversible dechelation and protonation of the pyridine N atoms, which enable an internal heterocoupling of a metal hydride and an N-bound proton to produce H₂

Tensor Perturbations in Quantum Cosmological Backgrounds

In the description of the dynamics of tensor perturbations on a homogeneous and isotropic background cosmological model, it is well known that a simple Hamiltonian can be obtained if one assumes that the background metric satisfies Einstein classical field equations. This makes it possible to analyze the quantum evolution of the perturbations since their dynamics depends only on this classical background. In this paper, we show that this simple Hamiltonian can also be obtained from the Einstein-Hilbert lagrangian without making use of any assumption about the dynamics of the background metric. In particular, it can be used in situations where the background metric is also quantized, hence providing a substantial simplification over the direct approach originally developed by Halliwell and Hawking.Comment: 24 pages, JHEP forma

Oxidized and reduced [2Fe-2S] clusters from an iron(I) synthon

© 2015 SBIC. Abstract Synthetic [2Fe-2S] clusters are often used to elucidate ligand effects on the reduction potentials and spectroscopy of natural electron-transfer sites, which can have anionic Cys ligands or neutral His ligands. Current synthetic routes to [2Fe-2S] clusters are limited in their feasibility with a range of supporting ligands. Here, we report a new synthetic route to synthetic [2Fe-2S] clusters, through oxidation of an iron(I) source with elemental sulfur. This method yields a neutral diketiminate-supported [2Fe-2S] cluster in the diiron(III)-oxidized form. The oxidized [2Fe-2S] cluster can be reduced to a mixed valent iron(II)-iron(III) compound. Both the diferric and reduced mixed valent clusters are characterized using X-ray crystallography, Mössbauer spectroscopy, EPR spectroscopy and cyclic voltammetry. The reduced compound is particularly interesting because its X-ray crystal structure shows a difference in Fe-S bond lengths to one of the iron atoms, consistent with valence localization. The valence localization is also evident from Mössbauer spectroscopy