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151.
AC Schmidt AV Nizovtsev A Scheurer FW Heinemann K Meyer 《Chemical communications (Cambridge, England)》2012,48(69):8634-8636
The new neopentyl (Neop)-substituted tris(aryloxide) U(iii) complex [(((Neop,Me)ArO)(3)tacn)U(III)] reacts with CO(2) to form CO and the bridging carbonate complex [{(((Neop,Me)ArO)(3)tacn)U(IV)}(2)(μ-CO(3))]. The uranium(iv) bridging oxo [{(((Neop,Me)ArO)(3)tacn)U(IV)}(2)(μ-O)] has been determined to be the intermediate in this reaction. For the first time, both U(iv) complexes can be reduced back to the U(iii) starting material. Thus, with KC(8) as reductant, [(((Neop,Me)ArO)(3)tacn)U(III)] engages in a synthetic cycle, in which CO(2) is converted to CO and CO(3)(2-). 相似文献
152.
A new family of tetranuclear nickel cube complexes [Ni(4)L(4)(solv)(4)] (1, solv = MeOH; 2, solv = H(2)O; H(2)L = pyrazole-based tridentate {ONO} ligand) has been studied in detail, in particular by X-ray diffraction and superconducting quantum interference device (SQUID) magnetometry. Different solvates 1·H(2)O, 2·4C(3)H(6)O, 2·CH(2)Cl(2), and 2·H(2)O were obtained in crystalline form. Only small structural variations were found for the Ni-O-Ni angles of the [Ni(4)O(4)] cores of those compounds, but these slight variations have dramatic consequences for the magnetic properties. [Ni(4)L(4)(MeOH)(4)]·H(2)O (1·H(2)O) and [Ni(4)L(4)(H(2)O)(4)]·H(2)O (2·H(2)O) can be reversibly interconverted in the solid state by exposure to the respective solvent, MeOH or H(2)O, and this goes along with a switching of the spin ground state from magnetic (S(T) = 4) to diamagnetic (S(T) = 0). Likewise the (irreversible) loss of lattice solvent in [Ni(4)L(4)(H(2)O)(4)]·4C(3)H(6)O (2·4C(3)H(6)O) to give 2·2C(3)H(6)O changes the ground state from S(T) = 4 to S(T) = 0. In view of these dramatic solvatomagnetic effects for the present [Ni(4)L(4)(solv)(4)] complexes, which occur upon extrusion of lattice solvent or facile exchange of coordinated solvent molecules while keeping the robust [Ni(4)O(4)] core intact, a note of care is issued: whenever magnetic data are obtained for powdered material or for crystals that easily loose lattice solvent molecules, the magnetic properties may not necessarily reflect the situation observed in the corresponding single crystal diffraction study. Finally, a thorough analysis of the present series of complexes as well as other {Ni(4)(μ(3)-OR)(4)} cubes reported in the literature confirms that a correlation between the (Ni-O-Ni)(av) bond angle and J in [Ni(4)O(4)] cubane complexes does indeed exist. 相似文献
153.
Neubert L Michalik D Bähn S Imm S Neumann H Atzrodt J Derdau V Holla W Beller M 《Journal of the American Chemical Society》2012,134(29):12239-12244
A novel and convenient protocol for the catalytic hydrogen-deuterium exchange of biologically active tertiary amines utilizing the borrowing hydrogen methodology has been developed. In the presence of the readily available Shvo catalyst, excellent chemoselectivity toward α- and β-protons with respect to the nitrogen atom as well as high degree of deuterium incorporation and functional group tolerance is achieved. This allowed for the deuteration of complex pharmaceutically interesting substrates, including examples for actual marketed drug compounds. Notably, this method constitutes a powerful tool for the generation of valuable internal standard materials for LC-MS/MS analyses highly demanded for various life-science applications. 相似文献
154.
Thevis M Beuck S Höppner S Thomas A Held J Schäfer M Oomens J Schänzer W 《Journal of the American Society for Mass Spectrometry》2012,23(3):537-546
Structure elucidation of steroids by mass spectrometry has been of great importance to various analytical arenas and numerous
studies were conducted to provide evidence for the composition and origin of (tandem) mass spectrometry-derived product ions
used to characterize and identify steroidal substances. The common product ion at m/z 97 generated from androst-4-ene-3-one analogs has been subject of various studies, including stable isotope-labeling and
(high resolution/high accuracy) tandem mass spectrometry, but its gas-phase structure has never been confirmed. Using high
resolution/high accuracy mass spectrometry and low resolution tandem mass spectrometry, density functional theory (DFT) calculation,
and infrared multiple photon dissociation (IRMPD) spectroscopy employing a free electron laser, the structure of m/z 97 derived from testosterone was assigned to protonated 3-methyl-2-cyclopenten-1-one. This ion was identified in a set of
six cyclic C6H9O+ isomers as computed at the B3LYP/6-311++G(2d,2p) level of theory (protonated 3-methyl-2-cyclopenten-1-one, 2-methyl-2-cyclopenten-1-one
and 2-cyclohexen-1-one). Product ions of m/z 97 obtained from MS2 and MS3 experiments of protonated 3-methyl-2-cyclopenten-1-one, 2-methyl-2-cyclopenten-1-one, 2-cyclohexen-1-one, and testosterone
corroborated the suggested gas-phase ion structure, which was eventually substantiated by IRMPD spectroscopy yielding a spectrum
that convincingly matched the predicted counterpart. Finally, the dissociation pathway of the protonated molecule of testosterone
to m/z 97 was revisited and an alternative pathway was suggested that considers the exclusion of C-10 along with the inclusion of
C-5, which was experimentally demonstrated with stable isotope labeling. 相似文献
155.
Sebastian O. Klemm Sascha E. Pust Achim Walter Hassel Jürgen Hüpkes Karl J. J. Mayrhofer 《Journal of Solid State Electrochemistry》2012,16(1):283-290
The processes during chemical and electrochemical etching of Al-doped ZnO are investigated utilizing a scanning flow cell
setup with online detection of dissolved Zn ions. The rate of chemical dissolution was found to be a linear function of buffer
and proton concentration in near neutral pH solutions according to a transport limited reaction. In contrast, electrochemical
etching is limited by the kinetics of the reaction and increases linearly with the imposed current density. Due to this fundamental
difference, the dissolution of Zn can be either uniform over the whole surface or highly localized at active sites like grain
boundaries. A combined approach of chemical etching and the well-controllable galvanostatic dissolution thus allows a fine
adjustment of the ZnO:Al surface texture for applications in silicon thin film photovoltaic cells in order to improve their
overall energy conversion efficiency. 相似文献
156.
In the course of our investigations on the synthesis of enantiomerically pure anthracycline antibiotics by incorporation of chiral building blocks we prepared the O-methyl 3-deoxy-2-C-ethylribopyranoside 1.1 The further synthetic plan required the conversion of 1 to the dithioacetal 2 followed by glycol cleavage to a partially protected 1,4-dialdehyde for coupling experiments to leucoquinizarine in a Marschalk reaction. However, the reaction sequence failed1 and optically active rhodomycinone had to be synthezised in a different way.2 A reinvestigation of the synthesis revealed that the thioacetalization of 1 using the acidic conditions recommended by Corey et al.3 did not yield the usual open chain dithioacetal 2 but rather three new unexpected products. The less polar fraction was identified by 1H and 13C NMR as tetrahydrofuran derivative 3a with the dithiane ring in a ß-orientation. The solid polar fraction (12%) consisted of a nonseparable 1:2.2 mixture of the epimeric deoxygenation products 4/5. 相似文献
157.
158.
Brückner R Haller H Ellwanger M Riedel S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(18):5741-5747
Polychloride monoanions stabilized by quaternary ammonium salts are investigated using Raman spectroscopy and state-of-the-art quantum-chemical calculations. A regular V-shaped pentachloride is characterized for the [N(Me)(4)][Cl(5)] salt, whereas a hockey-stick-like structure is tentatively assigned for [N(Et)(4)][Cl(2)???Cl(3)(-)]. Increasing the size of the cation to the quaternary ammonium salts [NPr(4)](+) and [NBu(4)](+) leads to the formation of the [Cl(3)](-) anion. The latter is found to be a pale yellow liquid at about 40 °C, whereas all the other compounds exist as powders. Further to these observations, the novel [Cl(9)](-) anion is characterized by low-temperature Raman spectroscopy in conjunction with quantum-chemical calculations. 相似文献
159.
Le Quement ST Flagstad T Mikkelsen RJ Hansen MR Givskov MC Nielsen TE 《Organic letters》2012,14(2):640-643
An application of readily available hydrazides in the Petasis 3-component coupling reaction is presented. An investigation of the substrate scope was performed to establish a general, synthetically useful protocol for the formation of hydrazido alcohols, which were selectively converted to oxazolidinone and oxadiazolone ring systems through triphosgene-mediated cyclization reactions. 相似文献
160.
Gansäuer A Knebel K Kube C van Gastel M Cangönül A Daasbjerg K Hangele T Hülsen M Dolg M Friedrich J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(9):2591-2599
The mechanism of catalytic 4-exo cyclizations without gem-dialkyl substitution was investigated by a comparison of cyclic voltammetry, EPR, and computational studies with previously published synthetic results. The most active catalyst is a super-unsaturated 13-electron titanocene(III) complex that is formed by supramolecular activation through hydrogen bonding. The template catalyst binds radicals via a two-point binding that is mandatory for the success of the 4-exo cyclization. The computational investigations revealed that formation of the observed trans-cyclobutane product is not possible from the most stable substrate radical. Instead, the most stable product is formed with the lowest energy of activation from a disfavored substrate in a Curtin-Hammett related scenario. 相似文献