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1.
Olaf Hübner Hans‐Jrg Himmel 《Angewandte Chemie (International ed. in English)》2020,59(29):12206-12212
Dinuclear compounds of early transition metals with a high metal–metal bond order are of fundamental interest due to their intriguing bonding situation and of practical interest because of their potential involvement in catalytic processes. In this work, two isomers of V2H2 have been generated in solid Ne by the reaction between V2 and H2 and detected by infrared spectroscopy: the linear HVVH molecule (3Σg? ground state), which is the product of the spin‐allowed reaction between V2 (3Σg? ground state) and H2, and a lower‐energy, folded V2(μ‐H)2 isomer (1A1 ground state) with two bridging hydrogen atoms. Both isomers are characterized by metal–metal bonding with a high bond order; the orbital occupations point to quadruple bonding. Irradiation with ultraviolet light induces the transformation of linear HVVH to folded V2(μ‐H)2, whereas irradiation with visible light initiates the reverse reaction. 相似文献
2.
Conrad Wagner Franka Kreis Dennis Popp Dr. Olaf Hübner Dr. Elisabeth Kaifer Prof. Hans-Jörg Himmel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(45):10336-10347
In this work, the change of reactivity induced by the introduction of two para-ethynyl substituents (CCSi(iPr)3 or CCH) to the organic electron-donor 1,2,4,5-tetrakis(tetramethylguanidino)-benzene is evaluated. The redox-properties and redox-state dependent fluorescence are evaluated, and dinuclear CuI and CuII complexes synthesized. The Lewis-acidic B(C6F5)3 substitutes the proton of the ethynyl −CCH groups to give new anionic −CCB(C6F5)3− substituents, leading eventually to a novel dianionic strong electron donor in its diprotonated form. Its two-electron oxidation with dioxygen in the presence of a copper catalyst yields the first redox-active guanidine that is neutral (instead of cationic) in its oxidized form. 相似文献
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4.
Analysis of a new drug of abuse: Cathinone derivative 1‐(3,4‐dimethoxyphenyl)‐2‐(ethylamino)pentan‐1‐one 下载免费PDF全文
Jennifer A. Weiß Magdalena Taschwer Olaf Kunert Martin G. Schmid 《Journal of separation science》2015,38(5):825-828
Recently, novel psychoactive drugs for human abuse such as amphetamines, phenethylamines, benzofuries, and tryptamines, cathinones have gained high popularity. These designer drugs are mainly sold via online stores as “bath salts” and are labeled “not for human consumption.” Due to the novelty of the compounds, only a little information about pharmacology, toxicology, and the long‐term damage they may cause is available. Moreover, there are only few analytical methods for their identification and analysis. Among new cathinone derivatives, 1‐(3,4‐dimethoxyphenyl)‐2‐(ethylamino)pentan‐1‐one (DL‐4662), became available via an internet shop. A sample of this compound was purchased and investigated. The first aim of our study was an identity check by NMR spectroscopy and gas chromatography with mass spectrometry. As many of the recreational drugs are chiral and are mainly sold as racemates, a further goal of our research was enantioseparation by gas chromatography with mass spectrometry and high‐performance liquid chromatography with UV detection, to prove whether DL‐4662 was traded enantiomerically pure or as racemic mixture. Both chiral separation methods showed the presence of a racemate. 相似文献
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6.
Dr. Olaf Morawski Dr. Paweł Gawryś Dr. Jarosław Sadło Prof. Andrzej L. Sobolewski 《Chemphyschem》2022,23(11):e202200077
When irradiated with violet light, hexaazatrinaphthylene (HATN) extracts a hydrogen atom from an alcohol forming a long-living hydrogenated species. The apparent kinetic isotope effect for fluorescence decay time in deuterated methanol (1.56) indicates that the lowest singlet excited state of the molecule is a precursor for intermolecular hydrogen transfer. The photochemical hydrogenation occurs in several alcohols (methanol, ethanol, isopropanol) but not in water. Hydrogenated HATN can be detected optically by an absorption band at 1.78 eV as well as with EPR (electron paramagnetic resonance) and NMR techniques. Mass spectrometry of photoproducts reveal di-hydrogenated HATN structures along with methoxylated and methylated HATN molecules which are generated through the reaction with methoxy radicals (remnants from alcohol splitting). Experimental findings are consistent with the theoretical results which predicted that for the excited state of the HATN-solvent molecular complex, there exists a barrierless hydrogen transfer from methanol but a small barrier for the similar oxidation of water. 相似文献
7.
Let Ω be an open, simply connected, and bounded region in \(\mathbb {R}^{d}\), d ≥ 2, and assume its boundary ?Ω is smooth and homeomorphic to \(\mathbb {S}^{d-1}\). Consider solving an elliptic partial differential equation L u = f(?, u) over Ω with zero Dirichlet boundary value. The function f is a nonlinear function of the solution u. The problem is converted to an equivalent elliptic problem over the open unit ball \(\mathbb {B}^{d}\) in \(\mathbb {R}^{d}\), say \(\widetilde {L}\widetilde {u} =\widetilde {f}(\cdot ,\widetilde {u})\). Then a spectral Galerkin method is used to create a convergent sequence of multivariate polynomials \(\widetilde {u} _{n}\) of degree ≤ n that is convergent to \(\widetilde {u}\). The transformation from Ω to \(\mathbb {B}^{d}\) requires a special analytical calculation for its implementation. With sufficiently smooth problem parameters, the method is shown to be rapidly convergent. For \(u\in C^{\infty } \left (\overline {\Omega }\right ) \) and assuming ?Ω is a C ∞ boundary, the convergence of \(\left \Vert \widetilde {u} -\widetilde {u}_{n}\right \Vert _{H^{1}}\) to zero is faster than any power of 1/n. The error analysis uses a reformulation of the boundary value problem as an integral equation, and then it uses tools from nonlinear integral equations to analyze the numerical method. Numerical examples illustrate experimentally an exponential rate of convergence. A generalization to ?Δu + γ u = f(u) with a zero Neumann boundary condition is also presented. 相似文献
8.
Steffen Blaurock Thomas Koch Olaf Kühl Peter Lönnecke Felicite Majoumo René Sommer 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1451-1456
Substituted bifunctional phosphorus-based ligands HX(CRR') n PR"H (or -PR" 2 ) [where X = O, S, NR', (substituted) cyclopentadienyl; n = 1, 2, 3; R, R', R" = alkyl, aryl, H] were employed as bridging ligands in the synthesis of early/late bridged transition metal complexes. Synthetic routes to the bifunctional ligands were also developed. First, mononuclear complexes, such as [TpZr(OCH 2 PPh 2 ) 3 ] (Tp = trispyrazolylborato), [Cp 2 Zr(1-O-2-PHR-C 6 H 10 )(Me)] (R = 2,4,6-Pr i 3 C 6 H 2 (Tipp)), [Cp 2 Zr(SCH 2 CH 2 PHR) 2 ] (R = Ph, Mes, Tipp), and phosphinoferrocene derivatives, were prepared. These complexes are suitable precursors for the introduction of a second metal (as in, for example, [TpZr( w -OCH 2 PPh 2 ) 3 Mo(CO) 3 ]). 相似文献
9.
Dr. Olaf Walter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(12):2927-2934
Recent developments and results from the organometallic chemistry of the actinides are reviewed. In the last one and a half years the structural data of about 15 organometallic complexes of transuranium actinides (Np or Pu) have been published, all involving π-ligands in the coordination sphere of the metal ion. On the basis of these data, a comparison of these molecules is presented. Depending on the steric demands of the ligands, effects like the actinide contraction seem to be stronger or weaker in the structural features. This indicates that the interplay between the actinide ion and the π-ligand is rather flexible, enabling the formation of stable bonds over a broad range of actinide ion oxidation states. 相似文献