Metal-free α-amination of secondary amines: Computational and experimental evidence for azaquinone methide and azomethine ylide intermediates

We have performed a combined computational and experimental study to elucidate the mechanism of a metal-free α-amination of secondary amines. Calculations predicted azaquinone methides and azomethine ylides as the reactive intermediates and showed that iminium ions are unlikely to participate in these transformations. These results were confirmed by experimental deuterium-labeling studies and the successful trapping of the postulated azomethine ylide and azaquinone methide intermediates. In addition, computed barrier heights for the rate-limiting step correlate qualitatively with experimental findings. © 2013 American Chemical Society

Practical Methods for Locating Abandoned Wells in Populated Areas

An estimated 12 million wells have been drilled during the 150 years of oil and gas production in the United States. Many old oil and gas fields are now populated areas where the presence of improperly plugged wells may constitute a hazard to residents. Natural gas emissions from wells have forced people from their houses and businesses and have caused explosions that injured or killed people and destroyed property. To mitigate this hazard, wells must be located and properly plugged, a task made more difficult by the presence of houses, businesses, and associated utilities. This paper describes well finding methods conducted by the National Energy Technology Laboratory (NETL) that were effective at two small towns in Wyoming and in a suburb of Pittsburgh, Pennsylvania

Dual-frequency VLBI study of Centaurus A on sub-parsec scales

Centaurus A is the closest active galactic nucleus. High resolution imaging using Very Long Baseline Interferometry (VLBI) enables us to study the spectral and kinematic behavior of the radio jet-counterjet system on sub-parsec scales, providing essential information for jet emission and formation models. Our aim is to study the structure and spectral shape of the emission from the central-parsec region of Cen A. As a target of the Southern Hemisphere VLBI monitoring program TANAMI (Tracking Active Galactic Nuclei with Milliarcsecond Interferometry), VLBI observations of Cen A are made regularly at 8.4 and 22.3 GHz with the Australian Long Baseline Array (LBA) and associated telescopes in Antarctica, Chile, and South Africa. The first dual-frequency images of this source are presented along with the resulting spectral index map. An angular resolution of 0.4 mas x 0.7 mas is achieved at 8.4 GHz, corresponding to a linear scale of less than 0.013 pc. Hence, we obtain the highest resolution VLBI image of Cen A, comparable to previous space-VLBI observations. By combining with the 22.3 GHz image, which has been taken without contributing transoceanic baselines at somewhat lower resolution, we present the corresponding dual-frequency spectral index distribution along the sub-parsec scale jet revealing the putative emission regions for recently detected gamma-rays from the core region by Fermi/LAT. We resolve the innermost structure of the milliarcsecond scale jet and counterjet system of Cen A into discrete components. The simultaneous observations at two frequencies provide the highest resolved spectral index map of an AGN jet allowing us to identify multiple possible sites as the origin of the high energy emission.Comment: 5 pages, 3 figures (1 color); A&A, accepte

Asymmetry in the Ligand Coordination Sphere of the [FeFe] Hydrogenase Active Site Is Reflected in the Magnetic Spin Interactions of the Aza-propanedithiolate Ligand

[FeFe] hydrogenases are very active enzymes that catalyze the reversible conversion of molecular hydrogen into protons and electrons. Their active site, the H-cluster, contains a unique binuclear iron complex, [2Fe](H), with CN- and CO ligands as well as an aza-propane-dithiolate (ADT) moiety featuring a central amine functionality that mediates proton transfer during catalysis. We present a pulsed C-13-ENDOR investigation of the H-cluster in which the two methylene carbons of ADT are isotope labeled with C-13. We observed that the corresponding two C-13 hyperfine interactions are of opposite sign and corroborated this finding using density functional theory calculations. The spin polarization in the ADT ligand is shown to be linked to the asymmetric coordination of the distal iron site with its terminal CN- and CO ligands. We propose that this asymmetry is relevant for the enzyme reactivity and is related to the (optimal) stabilization of the iron-hydride intermediate in the catalytic cycle

Redox-Neutral alpha-Sulfenylation of Secondary Amines: Ring-Fused N,S-Acetals

Secondary amines react with thiosalicylaldehydes in the presence of catalytic amounts of acetic acid to generate ring-fused N,S-acetals in redox-neutral fashion. A broad range of amines undergo alpha-sulfenylation, including challenging substrates such morpholine, thiomorpholine, and piperazines. Computational studies employing density functional theory indicate that acetic acid reduces the energy barriers of two separate steps, both of which involve proton transfer