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91.
The gallides SrRh2Ga2, SrIr2Ga2, and Sr3Rh4Ga4 were obtained from the elements by induction melting and subsequent annealing. They were investigated by powder and single‐crystal X‐ray diffraction: CaRh2B2 type, Fddd, a = 573.2(1), b = 1051.3(1), c = 1343.7(2) pm, wR2 = 0.0218, 398 F2 values, 15 variables for SrRh2Ga2; a = 576.0(1), b = 1045.5(1), c = 1350.6(3) pm for SrIr2Ga2, and Na3Pt4Ge4 type, I$\bar{4}$ 3m, a = 777.4(2) pm, wR2 = 0.0234, 190 F2 values, 11 variables for Sr3Ir4Ga4. The gallides SrRh2Ga2 and Sr3Ir4Ga4 exhibit complex, covalently bonded three‐dimensional [Rh2Ga2] and [Ir4Ga4] networks with short Rh–Ga (241–246 pm) and Ir–Ga (243–259 pm) distances. The strontium atoms fill large cages within these networks. They are coordinated by 8 Rh + 10 Ga in SrRh2Ga2 and by 4 Ir + 8 Ga in Sr3Ir4Ga4. The structure of SrRh2Ga2 is discussed along with the monoclinic distortion variants HoNi2B2 and BaPt2Ga2 on the basis of a group‐subgroup scheme. 相似文献
92.
Christian P. Sindlinger Sebastian Weiß Dr. Hartmut Schubert Prof. Dr. Lars Wesemann 《Angewandte Chemie (International ed. in English)》2015,54(13):4087-4091
NHC adducts of the stannylene Trip2Sn (Trip=2,4,6‐triisopropylphenyl) were reacted with zero‐valent Ni, Pd, and Pt precursor complexes to cleanly yield the respective metal complexes featuring a three‐membered ring moiety Sn‐Sn‐M along with carbene transfer onto the metal and complete substitution of the starting ligands. Thus the easily accessible NHC adducts to stannylenes are shown to be valuable precursors for transition‐metal complexes with an unexpected Sn? Sn bond. The complexes have been studied by X‐ray diffraction and NMR spectroscopy as well as DFT calculations. The compounds featuring the structural motif of a distannametallacycle comprised of a [(NHC)2M0] fragment and Sn2Trip4 represent rare higher congeners of the well‐known olefin complexes. DFT calculations indicate the presence of a π‐type Sn–Sn interaction in these first examples for acyclic distannenes symmetrically coordinating to a zero‐valent transition metal. 相似文献
93.
Total Synthesis of Albicidin: A Lead Structure from Xanthomonas albilineans for Potent Antibacterial Gyrase Inhibitors 下载免费PDF全文
Julian Kretz Dennis Kerwat Vivien Schubert Stefan Grätz Alexander Pesic Siamak Semsary Stéphane Cociancich Monique Royer Prof. Dr. Roderich D. Süssmuth 《Angewandte Chemie (International ed. in English)》2015,54(6):1969-1973
The peptide antibiotic albicidin, which is synthesized by the plant pathogenic bacterium Xanthomonas albilineans, displays remarkable antibacterial activity against various Gram‐positive and Gram‐negative microorganisms. The low amounts of albicidin obtainable from the producing organism or through heterologous expression are limiting factors in providing sufficient material for bioactivity profiling and structure–activity studies. Therefore, we developed a convergent total synthesis route toward albicidin. The unexpectedly difficult formation of amide bonds between the aromatic amino acids was achieved through a triphosgene‐mediated coupling strategy. The herein presented synthesis of albicidin confirms the previously determined chemical structure and underlines the extraordinary antibacterial activity of this compound. The synthetic protocol will provide multigram amounts of albicidin for further profiling of its drug properties. 相似文献
94.
Serge Schubert Philippe Renaud Pierre-Alain Carrupt Kurt Schenk 《Helvetica chimica acta》1993,76(7):2473-2489
Radical addition to enamines using Bu3SnH as reducing agent are reported (Schemes 2 and 4). The diastereoselectivity of these reactions was examined in different systems (Tables 1 and 2). Enamines derived from cyclic ketones such as cyclohexanone were alkylated with high diastereoselectivity with preferential formation of the cis-disubstituted cycloalkanes. In acyclic systems such as enamines derived from propiophenone and diethyl ketone, moderate to high stereoselectivities were observed in the H-abstraction step. A model based principally on minimization of allylic 1,3-strain (A1,3 strain) was deduced from the experimental results and semi-empirical (AM1) calculations. 相似文献
95.
Karsten Schubert Theodor Alpermann Tobias Niksch Helmar Grls Wolfgang Weigand 《无机化学与普通化学杂志》2006,632(6):1033-1042
Synthesis and Analytical Characterization of Functionalized β‐Hydroxydithiocinnamic Acids and their Esters. Complex Chemistry towards Nickel(II), Palladium(II), and Platin(II) Starting from silyl‐protected 4‐hydroxy acetophenone ( 1 ) the 1,1‐ethenedihiolato complexes 3 – 5 were synthesised using carbon disulfide and potassium‐tert‐butylate as a base. After being deprotected, the resulting 4‐hydroxy‐substituted complexes 6 – 8 were esterified with DL‐α‐lipoic acid to obtain the compounds 9 – 11 . The resulting complexes were characterized using NMR spectroscopy, mass spectrometry and IR spectroscopy. 3‐substituted β‐hydroxydithiocinnamic acid methyl ester ( 12 ) was obtained via an analogous path of reaction using silyl‐protected 3‐hydroxy acetophenone ( 2 ), carbon disulfide and methyl iodide. After removing of the silyl group the resulting hydroxy group was esterified with DL‐α‐lipoic acid. Using the dithioacid ester 14 as a ligand the NiII ( 15 ), PdII ( 16 ) and PtII ( 17 ) [O,S] complexes were obtained. 相似文献
96.
José Bonilla-Cruz Carlos Guerrero-Sánchez Ulrich S. Schubert Enrique Saldívar-Guerra 《European Polymer Journal》2010,46(2):298-4769
High-throughput experimentation was used for the functionalization of polybutadiene and polyisoprene with several kinds of nitroxide moieties at 135 °C, as well as for kinetic investigations of the controlled free radical grafting of styrene and maleic anhydride onto the functionalized polydienes at 125 °C. The functionalized polymers were analyzed by GPC, 1H NMR and FT-IR and the control of the grafting process was assessed by kinetic measurements and GPC analysis. The best control in the molecular weight of the grafts was observed for the polydienes functionalized with 4-oxo-TEMPO. TEMPO functionalization did not render sufficient nitroxide moieties to achieve controlled grafting, while polydienes functionalized with other 4-hydroxy TEMPO derivatives exhibited some level of grafting control at early reaction times, which was lost in later stages of the polymerization reaction. SG1 apparently decomposed at the tested reaction temperatures, as polydienes functionalized with SG1 did not show any level of control during the grafting process. 相似文献
97.
Molecular dynamics simulations with atomistic detail of the gel phase and melting transitions of dipalmitoyl phosphatidylcholine bilayers in water reveal the dependency of many thermodynamic and structural parameters on the initial system ordering. We quantitatively compare different methods to create a gel phase system and we observe that a very high ordering of the gel phase starting system is necessary to observe behavior which reproduces experimental data. We performed heating scans with speeds down to 0.5 K/ns and could observe sharp first order phase transitions. Also, we investigated the transition enthalpy as the natural intrinsic parameter of first order phase transitions, and obtained a quantitative match with experimental values. Furthermore, we performed systematic investigations of the statistical distribution and heating rate dependency of the microscopic phase transition temperature. 相似文献
98.
Glassner M Kempe K Schubert US Hoogenboom R Barner-Kowollik C 《Chemical communications (Cambridge, England)》2011,47(38):10620-10622
An efficient method for the preparation of cyclopentadienyl endcapped poly(2-ethyl-2-oxazoline) (PEtOx-Cp) via cationic ring-opening polymerization utilizing sodium cyclopentadienide as a termination agent is presented. Subsequent Diels-Alder reactions with N-substituted maleimides proceed quantitatively at ambient temperature. A block copolymer (PEtOx-b-PEG) is prepared employing maleimide terminated poly(ethylene glycol). 相似文献
99.
Siebert R Winter A Schubert US Dietzek B Popp J 《Physical chemistry chemical physics : PCCP》2011,13(4):1606-1617
Temperature dependent luminescence experiments are combined with femtosecond time-resolved transient absorption spectroscopy to decipher the photoinduced excited-state relaxation pathway in mononuclear Fe, Ru and Os terpyridine complexes bearing a conjugated chromophore within the ligand framework. The herein presented complexes constitute a class of coordination compounds, which overcome the poor emission properties commonly observed for most terpyridine transition metal complexes. As reported earlier, the complexes reveal dual emission at room temperature stemming from ligand centered and metal-to-ligand charge-transfer states. The molecular mechanism of the room temperature dual luminescence is addressed experimentally in this contribution. The experimental results indicate an ultrafast branching reaction within the excited-state manifold upon photoexcitation of the ligand-centered S(1) state. This branching occurs from a "hot" excited state geometry close to the Franck-Condon point of absorption and within ~100 fs, i.e. the temporal resolution of our experimental setup. The combination of ultrafast differential absorption experiments and temperature-dependent luminescence data allows not only to draw conclusions about the molecular mechanism underlying the observed dual emission but also to construct quantitative Jablonski diagrams and, thereby, to detail the excited-state topology determining the remarkable luminescence properties of the systems at hand. 相似文献
100.
Thorwirth R Stolle A Ondruschka B Wild A Schubert US 《Chemical communications (Cambridge, England)》2011,47(15):4370-4372
A new, ligand- and solvent-free method for the Huisgen 1,3-dipolar cycloaddition (click reaction) was developed using a planetary ball mill. Besides various alkynes and azides, a propargyl functionalized polymer was converted by mill clicking. Moreover, it was possible to carry out a click polymerization in a ball mill. 相似文献