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991.
Mulhern D Brooker S Görls H Rau S Vos JG 《Dalton transactions (Cambridge, England : 2003)》2006,(1):51-57
A novel, and quite general, approach for the preparation of tris(heteroleptic) ruthenium(II) complexes is reported. Using this method, which is based on photosubstitution of carbonyl ligands in precursors such as [Ru(bpy)(CO)(2)Cl(2)] and [Ru(bpy)(Me(2)bpy)(CO)(2)](PF(6))(2), mononuclear and dinuclear Ru(II) tris(heteroleptic) polypyridyl complexes containing the bridging ligands 3,5-bis(pyridin-2-yl)-1,2,4-triazole (Hbpt) and 3,5-bis(pyrazin-2-yl)-1,2,4-triazole (Hbpzt) have been prepared. The complexes obtained were purified by column chromatography and characterized by HPLC, mass spectrometry, 1H NMR, absorption and emission spectroscopy and by electrochemical methods. The X-ray structures of the compounds [Ru(bpy)(Me(2)bpy)(bpt)](PF(6))x0.5C(4)H(10)O [1x0.5C(4)H(10)O], [Ru(bpy)(Me(2)bpy)(bpzt)](PF(6))xH(2)O (2xH(2)O) and [Ru(bpy)(Me(2)bpy)(CH(3)CN)(2)](PF(6))(2)xC(4)H(10)O (6xC(4)H(10)O) are reported. The synthesis and characterisation of the dinuclear analogues of 1 and 2, [{Ru(bpy)(Me(2)bpy)}(2)bpt](PF(6))(3)x2H(2)O (3) and [{Ru(bpy)(Me(2)bpy)}(2)bpzt](PF(6))(3) (4), are also described. 相似文献
992.
Tobisch S 《Dalton transactions (Cambridge, England : 2003)》2006,(35):4277-4285
The complete sequence of steps of a tentative catalytic cycle for intramolecular hydroamination/cyclisation (IHC) of 4,5-hexadien-1-ylamine (1) by a prototypical cationic [Cp(2)ZrCH(3)](+) zirconocene precatalyst (2) has been examined by employing a gradient-corrected DFT method. The predicted smooth overall reaction energy profile is consistent with the available experimental data, thereby providing further confidence in the proposed mechanism. Following activation of the precatalyst by protonolytic cleavage of the Zr-Me bond, the catalytically active amidoallene-Zr complex undergoes addition of an allenic C[double bond, length as m-dash]C linkage across the Zr-N sigma-bond. The alternative exo- and endocyclic pathways show similar probabilities for the sterically less encumbered reactants {1 + 2} investigated herein. However, steric factors are expected to exert control on the regioselectivity of ring closure. On the other hand, the metathesis-type transition states for subsequent protonolysis are indicated to be less sensitive to steric demands. Formation of the six-membered azacycle-Zr intermediate through intramolecular C[double bond, length as m-dash]C insertion into the Zr-N sigma-bond is predicted to be turnover limiting. The factors that govern the regioselectivity of the aminoallene IHC have been elucidated. 相似文献
993.
The X-ray absorption near-edge structures (XANES) at the F K-edge of alpha-AlF(3), beta-AlF(3) and a tetragonal AlF(3) phase are analysed by a combination of ab initio calculations with the FEFF8 code and a phenomenological discussion of local molecular orbital (MO) symmetries at the absorbing fluorine atoms. By means of a Walsh correlation diagram it is shown that the two intense absorption bands observed at the F K-edges of the AlF(3) polymorphs can be interpreted as transitions to anti-bonding MOs in [Al-F-Al]-units that have C(2v) and D(infinity h) point group symmetries. The energies of both anti-bonding orbitals are very insensitive to the angle between the Al-F bonds, which explains the close similarity of the XANES signatures from the three polymorphs. The FEFF8 analysis shows that the increased broadening of the XANES structure for beta-AlF(3) and the tetragonal AlF(3) phase is due to the superposition of the individual absorption spectra from the crystallographically distinct F species. The interpretation in terms of local MOs provides for the first time a "chemically intuitive" approach to investigations of solid fluorides by XANES spectroscopy and provides a simple conceptual framework for the discussion of the electronic structure in AlF(3) materials. 相似文献
994.
995.
[reaction: see text] (-)-(5S)-2-Imino-1-methylpyrrolidine-5-carboxylic acid (1), previously reported as the N-acetyl-beta-d-glucosaminidase inhibitor pyrostatin B, has been isolated from the organic extracts of the burrowing sponge Cliona tenuis. The structure of 1, including its absolute stereochemistry, was characterized from its spectral data and chemical transformations and confirmed by total synthesis. The synthesis of 1 reveals that the structure of pyrostatin B has been incorrectly assigned. Comparison of NMR spectral data strongly suggests that pyrostatins A and B are identical to 5-hydroxyectoine and ectoine, respectively. 相似文献
996.
[reaction: see text] Reaction of chiral alpha-chloro tert-butanesulfinyl aldimines with Grignard reagents efficiently afforded beta-chloro N-sulfinamides in high diastereomeric excess. The latter compounds were cyclized toward the corresponding chiral aziridines in a high-yielding one-pot reaction or after separate treatment with base. The diastereoselectivity obtained in the newly synthesized beta-chloro sulfinamides is explained via the coordinating ability of the alpha-chloro atom with magnesium resulting in the opposite stereochemical outcome as generally observed for nonfunctionalized N-sulfinyl imines. 相似文献
997.
Serneels S De Nolf E Van Espen PJ 《Journal of chemical information and modeling》2006,46(3):1402-1409
The spatial sign is a multivariate extension of the concept of sign. Recently multivariate estimators of covariance structures based on spatial signs have been examined by various authors. These new estimators are found to be robust to outlying observations. From a computational point of view, estimators based on spatial sign are very easy to implement as they boil down to a transformation of the data to their spatial signs, from which the classical estimator is then computed. Hence, one can also consider the transformation to spatial signs to be a preprocessing technique, which ensures that the calibration procedure as a whole is robust. In this paper, we examine the special case of spatial sign preprocessing in combination with partial least squares regression as the latter technique is frequently applied in the context of chemical data analysis. In a simulation study, we compare the performance of the spatial sign transformation to nontransformed data as well as to two robust counterparts of partial least squares regression. It turns out that the spatial sign transform is fairly efficient but has some undesirable bias properties. The method is applied to a recently published data set in the field of quantitative structure-activity relationships, where it is seen to perform equally well as the previously described best linear model for these data. 相似文献
998.
Kshitij Sanjay Shinde Philipp Michael Michael Rössle Sven Thiele Wolfgang H. Binder 《Journal of polymer science. Part A, Polymer chemistry》2020,58(20):2864-2874
The incorporation of functional groups into unsaturated polyolefine-polymers often represent a challenging task. Based on the known cyclopropanation of double bonds with diazoesters in the presence of metal-catalysts of low molecular weight compounds, we in this article develop an approach to decorate the polymer backbone of poly(diene)s with ester as well as carboxylic groups via cyclopropanation. Therefore, predominantly cis-1,4-poly(isoprene)s are converted with ethyl or tert-butyl diazoacetate using copper(I) N-heterocyclic carbene (NHC) catalysts, while focusing on the technically relevant cyclohexane as solvent. The application of commercially available NHC-Cu(I) catalysts results in modification degrees of 4–5%, while an increased solvent polarity, like dichloromethane, results in up to 17% modification. The resulting esters were further converted to the corresponding free carboxylic groups by deprotection using trifluoroacetic acid. Thus, an introduction of functional groups along the polymer backbone with a wide variety of application, like ionic interaction or hydrogen bonding motifs, was successfully demonstrated. Its potential for upscaling makes this approach feasible for an application in large-scale production processes, such as for manufacturing of modified synthetic rubbers. 相似文献
999.
Xuelin Fan Swen Zerebecki Ran Du René Hübner Galina Marzum Guocan Jiang Yue Hu Stephan Barcikowki Sven Reichenberger Alexander Eychmüller 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(14):5755-5760
Noble metal aerogels (NMAs) are an emerging class of porous materials. Embracing nano-sized highly-active noble metals and porous structures, they display unprecedented performance in diverse electrocatalytic processes. However, various impurities, particularly organic ligands, are often involved in the synthesis and remain in the corresponding products, hindering the investigation of the intrinsic electrocatalytic properties of NMAs. Here, starting from laser-generated inorganic-salt-stabilized metal nanoparticles, various impurity-free NMAs (Au, Pd, and Au-Pd aerogels) were fabricated. In this light, we demonstrate not only the intrinsic electrocatalytic properties of NMAs, but also the prominent roles played by ligands in tuning electrocatalysis through modulating the electron density of catalysts. These findings may offer a new dimension to engineer and optimize the electrocatalytic performance for various NMAs and beyond. 相似文献
1000.
Jens Bielefeld Sven Doye 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(15):6194-6199
The scientific interest in catalytic hydroaminoalkylation reactions of alkenes has vastly increased over the past decade, but these reactions have struggled to become a viable option for general laboratory or industrial use because of reaction times of several days. The titanium-based catalytic system introduced in this work not only reduces the reaction time by several orders of magnitude, into the range of minutes, but the catalyst is also demonstrated to be easily available from common starting materials, at a cost of approximately 1 € per millimole of catalyst. We were also able to formally perform C−H activation of methylamine and achieve coupling to a broad variety of alkenes, through silyl protection of the amine and simple deprotection by water. 相似文献