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31.
Combining Experimental and Computational Studies to Understand and Predict Reactivities of Relevance to Homogeneous Catalysis 下载免费PDF全文
Dr. Althea S.‐K. Tsang Italo A. Sanhueza Prof. Dr. Franziska Schoenebeck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16432-16441
This article showcases three major uses of computational chemistry in reactivity studies: the application after, in combination with, and before experiment. Following a brief introduction of suitable computational tools, challenges and opportunities in the implementation of computational chemistry in reactivity studies are discussed, exemplified with selected case studies from our and other laboratories. 相似文献
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Gizem Dübek Franziska Hanusch Dominik Munz Shigeyoshi Inoue 《Angewandte Chemie (International ed. in English)》2020,59(14):5823-5829
Air‐ and moisture‐stable heterobimetallic tetrahedral clusters [Cp(CO)2MSiR]2 (M=Mo or W; R=SitBu3) were isolated from the reaction of N‐heterocyclic carbene (NHC) stabilized silyl(silylidene) metal complexes Cp(CO)2M=Si(SitBu3)NHC with a mild Lewis acid (BPh3). Alternatively, treatment of the NHC‐stabilized silylidene complex Cp(CO)2W=Si(SitBu3)NHC with stronger Lewis acids such as AlCl3 or B(C6F5)3 resulted in the reversible coordination of the Lewis acid to one of the carbonyl ligands. Computational investigations revealed that the dimerization of the intermediate metal silylidyne (M≡Si) complex to a tetrahedral cluster instead of a planar four‐membered ring is due to steric bulk. 相似文献
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In order to treat one-parameter semigroups of linear operators on Banach spaces which are not strongly continuous, we introduce the concept of bi-continuous semigroups defined on Banach spaces with an additional locally convex topology . On such spaces we define bi-continuous semigroups as semigroups consisting of bounded linear operators which are locally bi-equicontinuous for and such that the orbit maps are -continuous. We then apply the result to semigroups induced by flows on a metric space as studied by J. R. Dorroh and J. W. Neuberger. 相似文献
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Franziska Emmerling Caroline Röhr 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(10):1127-1128
The two title trialkaline trioxoantimonates(III), tripotassium trioxoantimonate(III), K3[SbO3], (I), and tricaesium trioxoantimonate(III), Cs3[SbO3], (II), crystallize in the cubic Na3[AsS3] structure type in space group P213. The structures show discrete Ψ-tetrahedral [SbO3]3− anions with C3v point-group symmetry. The Sb—O distances are 1.923 (4) Å in (I) and 1.928 (2) Å in (II), and the O—Sb—O bond angles are 99.5 (2)° in (I) and 100.4 (1)° in (II). 相似文献
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Franziska Reuß Klaus‐Peter Zeller Hans‐Ullrich Siehl Stefan Berger Dieter Sicker 《Chemie in Unserer Zeit》2016,50(3):198-208
The diterpene glycoside stevioside is the most abundant among a group of sweet steviol glycosides, present in sweetleaf (Stevia rebaudiana), which is naturally occurring in Paraguay. It has already been used by the Guarani Indians as a sweetener. Since 2011 such “steviosides” have an EU approval as sweeteners E 960. They taste ca. 250 times sweeter than sucrose. Meanwhile, they have got a significant recognition, not least due to their use in Coca Cola life®. We describe the isolation of stevioside and rebaudioside A from dried leaves of the sweetleaf plant. The complete set of spectra for stevioside is reported. Based on students' laboratory work this project is a follow up of the book “Classics in Spectroscopy” by S. Berger und D. Sicker (Wiley‐VCH 2009). 相似文献
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Cationic,Methylene‐Bridged,Intramolecular Donor‐Acceptor Systems Based on Zirconium and Hafnium and Phosphino‐methanides 下载免费PDF全文
Martin Pieper Pauline Auer Sabrina Schwarzbich Franziska Kühn Beate Neumann Hans‐Georg Stammler Norbert W. Mitzel 《无机化学与普通化学杂志》2017,643(14):909-915
A new access to cationic zirconium and hafnium compounds [L2MCH2PR2][MeB(C6F5)3] (L = Cp, Ind; R = iso‐Pr, tert‐Bu; M = Zr, Hf) exhibiting an intramolecular donor‐acceptor system was established by treating the precursors L2M(Me)CH2PR2 with B(C6F5)3 (BCF). Precursors 1 – 6 [L2M(Me)CH2PR2 with L = Cp, Ind; R = iso‐Pr, tert‐Bu; M = Zr, Hf] were fully characterized. The crystal structures of these compounds revealed large M–CH2–P bond angles with values of about 134° indicating the absence of interactions between the Lewis‐acid and Lewis‐base. The cationic compounds [L2MCH2PR2][MeB(C6F5)3] ( 7 – 12 ) were obtained by treatment of 1 – 6 with BCF. They were characterized by NMR spectroscopy, mass spectrometry, and elemental analyses; in H/D‐scrambling experiments with H2/D2 mixtures 7 – 12 disclosed their reactivity towards cleavage of hydrogen. 相似文献
40.
Franziska Gruber Martin Schulz‐Dobrick Dr. Martin Jansen Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(5):1464-1469
Crystallization of [Ag14(C?CtBu)12Cl][BF4] and different polyoxometalates in organic solvents yields a series of new intercluster compounds: [Ag14(C?CtBu)12Cl(CH3CN)]2[W6O19] ( 1 ), (nBu4N)[Ag14(C?CtBu)12Cl(CH3CN)]2[PW12O40] ( 2 ), and [Ag14(C?CtBu)12Cl]2[Ag14(C?CtBu)12Cl(CH3CN)]2[SiMo12O40] ( 3 ). Applying the same technique to a system starting from polymeric {[Ag3(C?CtBu)2][BF4]?0.6 H2O}n and the polyoxometalate (nBu4N)2[W6O19] results in the formation of [Ag14(C?CtBu)12(CH3CN)2][W6O19] ( 4 ). Here, the Ag14 cluster is generated from polymeric {[Ag3(C?CtBu)2][BF4]?0.6 H2O}n during crystallization. In a similar way, [Ag15(C?CtBu)12(CH3CN)5][PW12O40] ( 5 ) has been obtained from {[Ag3(C?CtBu)2][BF4]?0.6 H2O}n and (nBu4N)3[PW12O40]. The use of charged building blocks was intentional, because at these conditions the contribution of long‐range Coulomb interactions would benefit most from full periodicity of the intercluster compound, thus favoring formation of well‐crystalline materials. The latter has been achieved, indeed. However, as a most conspicuous feature, equally charged species aggregate, which demonstrates that the short‐range interactions between the “surfaces” of the clusters represent the more powerful structure direction forces than the long‐range Coulomb bonding. This observation is of significant importance for understanding the mechanisms underlying self‐organization of monodisperse and structurally well‐defined particles of nanometer size. 相似文献