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41.
Decay of Iron(V) Nitride Complexes By a NN Bond‐Coupling Reaction in Solution: A Combined Spectroscopic and Theoretical Analysis 下载免费PDF全文
Oliver Krahe Dr. Eckhard Bill Prof. Dr. Frank Neese 《Angewandte Chemie (International ed. in English)》2014,53(33):8727-8731
Cryogenically trapped FeV nitride complexes with cyclam‐based ligands were found to decay by bimolecular reactions, forming exclusively FeII compounds. Characterization of educts and products by Mössbauer spectroscopy, mass spectrometry, and spectroscopy‐oriented DFT calculations showed that the reaction mechanism is reductive nitride coupling and release of dinitrogen (2 FeV?N→FeII‐N?N‐FeII→2 FeII+N2). The reaction pathways, representing an “inverse” of the Haber–Bosch reaction, were computationally explored in detail, also to judge the feasibility of yielding catalytically competent FeV(N). Implications for the photolytic cleavage of FeIII azides used to generate high‐valent Fe nitrides are discussed. 相似文献
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Dipl.‐Chem. Fabian Schax Dr. Eckhard Bill Dr. Christian Herwig Prof. Dr. Christian Limberg 《Angewandte Chemie (International ed. in English)》2014,53(47):12741-12745
The reaction of a tripodal trisilanol with n‐butyllithium and CrCl2 results in a dinuclear CrII complex ( 1 ), which is capable of cleaving O2 to yield in a unique complex ( 2 ) with an asymmetric diamond core composed of two CrIV?O units. Magnetic susceptibility data reveal significant exchange coupling of CrII (S=2) in 1 and large zero‐field splitting for CrIV (S=1) in 2 owing to strong spin–orbit coupling of the ground state. The CrIV?O compound can also be generated using PhIO, and evidence was gathered that although it is the stable product isolated after excessive O2 treatment, it further activates O2 to yield an intermediate species that oxidizes THF or Me‐THF. By extensive 18O labeling studies we were able to show, that in the course of this process 18O2 exchanges its label with siloxide O atoms of the ligand via terminal oxido ligands. 相似文献
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Glow discharge spectroscopy (GDOS) will be shown to be a quick, informative and simple method for quantitative depth profile analysis of elements of nitrided layers well suited for their quality control. By systematic variation of all glow discharge determining parameters it is possible to get an excellent depth resolution in the order of sub-m corresponding to a comparatively large analytical activated area (50 mm2). In this paper the behaviour of a number of important parameters related to sputtering of the activated area will be discussed. Some quantitative GDOS depth profiles of carbon and nitrogen of pure iron samples nitrided by different procedures will be shown as examples for application. 相似文献
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A new, sensitive assay for the quantitative determination of immobilized metal containing enzymes has been developed using atomic absorption spectroscopy (AAS). In contrast with conventionally used indirect methods the described quantitative AAS assay for metalloenzymes allows more exact analyses, because the carrier material with the enzyme is investigated directly. As an example, the validity and reliability of the method was examined by fixing the iron-containing enzyme catalase on cotton fabrics using different immobilization techniques. Sample preparation was carried out by dissolving the loaded fabrics in sulfuric acid before oxidising the residues with hydrogen peroxide. The iron concentrations were determined by flame atomic absorption spectrometry after calibration of the spectrometer with solutions of the free enzyme at different concentrations. 相似文献
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Summary. A mixed finite element discretization is applied to Richards equation, a nonlinear, possibly degenerate parabolic partial differential equation modeling water flow through porous medium. The equation is considered in its pressure formulation and includes both variably and fully saturated flow regime. Characteristic for such problems is the lack in regularity of the solution. To handle this we use a time-integrated scheme. We analyze the scheme and present error estimates showing its convergence.Mathematics Subject Classification (2000): 65M12, 65M60, 76S05, 35K65Acknowledgments. We would like to thank Markus Bause for very useful discussions and suggestions. 相似文献