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31.
Eva BeckerChristian Slugovc Eva RübaChristina Standfest-Hauser Kurt MereiterRoland Schmid Karl Kirchner 《Journal of organometallic chemistry》2002,649(1):55-63
The synthesis and some reactions of the Ru(II) and Ru(IV) half-sandwich complexes [RuCp(EPh3)(CH3CN)2]+ (E=P, As, Sb, Bi) and [RuCp(EPh3)(η3-C3H5)Br]+ have been investigated. The chemistry of this class of compounds is characterized by a competitive coordination of EPh3 either via a RuE or a η6-arene bond, where the latter is favored when the former is weaker, that is in going down the series. Thus in the case of Bi, the starting material [RuCp(CH3CN)3]+ does not react with BiPh3 to give [RuCp(BiPh3)(CH3CN)2]+ but instead gives only the η6-arene species [RuCp(η6-PhBiPh2)]+ and [(RuCp)2(μ-η6,η6-Ph2BiPh)]2+. Similarly, the EPh3 ligand can be replaced by an aromatic solvent or an arene substrate. Thus, the catalytic performance of [RuCp(EPh3)(CH3CN)2]+ for the isomerization of allyl-phenyl ethers to the corresponding 1-propenyl ethers is best with E=P, while the conversion drops significantly using the As and Sb derivatives. By the same token, only [RuCp(PPh3)(CH3CN)2]+ is stable in a non-aromatic solvent, whereas both [RuCp(AsPh3)(CH3CN)2]+ and [RuCp(SbPh3)(CH3CN)2]+ rearrange upon warming to [RuCp(η6-PhEPh2)]+ and related compounds. In addition, the potential of [RuCp(EPh3)(CH3CN)2]+ as precatalysts for the transfer hydrogenation of acetophenone and cyclohexanone has been investigated. Again aromatic substrates are clearly less suited than non-aromatic ones due to facile η6-arene coordination leading to catalyst's deactivation. 相似文献
32.
Silvia E. Braslavsky Alfred R. Holzwarth Harald Lehner Kurt Schaffner 《Helvetica chimica acta》1978,61(6):2219-2222
Freshly prepared solutions of biliverdin dimethyl ester ( 2 ) in ethanol showed fluorescence maxima at 710 and 770 nm [ΦF = 1.1. 10?4 (room temperature) and 5.0 10?4 (77 K)]. The maxima of monoprotonated 2 at 77 K were shifted to 725 and 806 nm and the quantum yield was increased to 2.6. 10?2. This acid effect was reversible by neutralization with base. When a neutral solution was kept standing in the dark at room temperature, or when an acidic solution was neutralized by base, an additional fluorescence maximum at 500 nm with a mirror image excitation spectrum with λmax = 470 nm developed, which disappeared on addition of acid and which is attributed to a chemical change of 2 . 相似文献
33.
The enantiomerically pure (+)-3-methoxy-1, 3, 5 (10)-estratrien-11, 17-dione 11 (with trans-anti-trans configuration) was synthesized in a highly stereocontrolled fashion from (±)-t-butyl 4-methoxy-1-benzocyclobutene carboxylate (8) and the (+)-carboxylic acid 6 , obtained from 4 in two steps, followed by one crystallization of the (+)-ephedrine salt. The key step 10→11 (Scheme 2) involves a thermal intramolecular cycloaddition reaction. 相似文献
34.
Peter Lindemann Silvia E. Braslavsky Marie-Michle Cordonnier Lee H. Pratt Kurt Schaffner 《Photochemistry and photobiology》1993,58(3):417-424
Abstract–Thc kinetics of the microsecond phototransformation intermediates of 124 kDa Avena phytochrome (17001,2) were studied in the prcsence of bound monoclonal antibodies at various temperatures. A global analysis was applied to the decays at all wavelengths at each temperature in order to derive the rate constants and the decay-associated spectra of the three decay components. Monoclonal antibodies bound to specific epitopes altered the Arrhenius parameters of both 17001,2 decay components. The strongest influence on these parameters was observed with OAT 8 (epitope between residues 624 and 686), which decreased by more than 50% the activation parameters of both components. This decrease is interpreted to result from an increased flexibility induced by this antibody in the ground state or in the transition state of bonds changing during the decay of both 1700 transients. Thus, the OAT 8 cpitope appears to be functionally important during the decay of the 17001,2 intermediates. For the case of 11001 bound OAT 23 and OAT 25 (epitopes between residues 1 and 66) reduced even further the relatively small flexibility of these bonds in the red light-absorbing form of phytochrome (P1) without antibodies, as reflected by the high preex-ponential factors for its decay. This resulted also in higher activation energies for this decay in the presence of the antibodies. Thus, the amino-terminus should act as a rigid spacer of the chromophore cavity without affecting it during the microsecond transformation, because the Arrhenius parameters for these decays are similar to those for small phytochrome. The possible implications of the influence of the various antibodies on the bleaching remaining after the decay of 17001,2 are discussed. 相似文献
35.
Synthesis and Properties of Di-molybdenum-μ-nitrido-heptachloride, Mo2NCl7 Mo2NCl7 was prepared by the reaction of molybdenum pentachloride with the bromide of Millon's base, [Hg2N]Br, in boiling CCl4. It forms a moisture sensitive, dark green crystal powder, the magnetic moment at 20°C (μeff = 0.95 B.M.) being strongly reduced. With acetonitrile the μ-nitrido complex Mo2NCl7 · 3CH3CN is formed, with phosphoryl chloride the donor acceptor complex Mo2NCl7 · 2POCl3, respectively. Partial oxidation of the latter complex with chlorine leads to very unstable Mo2NCl8 · 2POCl3, from which (PPh4)3[Mo3NCl10] can be obtained by the reaction with PPh4Cl. For the complex (PPh4)3[Mo2NCl10] is also found a reduced paramagnetism of μeff = 1.47 B.M. at 20°C. All complexes are characterized by i.r. spectroscopy. 相似文献
36.
Y. D. Kurt G. S. Pozan İ. Kızılcıklı B. Ülküseven 《Russian Journal of Coordination Chemistry》2007,33(11):844-849
Mixed ligand complexes of dioxomolybdenum(VI) with 2-hydroxybenzaldehyde 4-phenyl-S-methylthiosemicarbazone (H2L) were prepared with the formula [MoO2(L)D] (D = H2O, methyl, n-butyl, and n-undecyl alcohol, DMF, DMSO, pyridine, 4-picoline, and 3,5-lutidine). The compounds were characterized by elemental
analysis, IR and 1H NMR spectroscopy. The thermal decomposition of the compounds were investigated by using TGA, DTG, and DTA methods in air,
and the thermal behavior depending on the second ligand molecule was discussed. A single crystal of the DMF coordinated complex
was studied by X-ray diffractometry.
The text was submitted by the authors in English. 相似文献
37.
Red and yellow dichroistic crystals of a vanadium(V) compound, potassium (mu-oxo, di-mu-sulfato)bis(oxodisulfatovanadate), K(8)(VO)(2)O(SO(4))(6), have been obtained from the ternary catalytic model melt system K(2)S(2)O(7)[bond]K(2)SO(4)[bond]V(2)O(5). By slow cooling of the melt from 420 to 355 degrees C, crystal growth occurred, using solid V(2)O(5) crystals present in the melt as nucleation promoter. The compound crystallizes in the monoclinic space group P2(l) with a = 13.60(9) A, b = 13.93(9) A, c = 14.05(9) A, beta = 90.286(10) degrees, and Z = 2. It contains two VO(6) octahedra linked together by a mu-oxo and two mu-sulfato bridges. Furthermore, each octahedron has two monodentate sulfate ligands, making the dimeric entity coordinatively saturated. IR spectroscopy shows bands arising from V[bond]O[bond]V and V[double bond]O stretches as well as splitting of sulfate bands due to the different degrees of freedom present for different conformations of sulfate ligands. The coordination of vanadium in K(8)(VO)(2)O(SO(4))(6) is discussed in relation to the reaction mechanism of SO(2) oxidation catalysis. 相似文献
38.
Kurt Rüfenacht 《Helvetica chimica acta》1975,58(6):1521-1527
Aza-analogues of the known pesticidal dithiophosphates 2, 4 and 5 have been prepared by replacing the phthalimide, benzotriazole and 1,2,3-benzotriazin-4(3H)-one moieties resp. in 2 by those of quinolinic acid imide (6), cinchomeronic acid imide (7) and pyrazine-2,3-dicarboxylic acid imide (12), in 4 by 1H-v-triazolo[4,5-b]pyridine (15) and in 5 by pyrido[2,3-e]1,2,3-triazin-4(3H)-one (21). Compared to the known compounds the new esters are less or at best equally pesticidal with an equal or even higher mammalian toxicity. 相似文献
39.
40.
Prasad V. S. Ika Harry L. Frisch Kurt C. Frisch 《Journal of polymer science. Part A, Polymer chemistry》1985,23(4):1163-1173
The synthesis of crosslinked polydiacetylenes and its two-component interpenetrating polymer networks (IPNs) was carried out utilizing its polar and flexible substituent groups. Polydiacetylenes were crosslinked by the formation of allophanate linkages utilizing urethane groups in the substituent groups of the polydiacetylenes. Elemental analysis, DSC, TMA, solvent resistance, and IR spectra are presented as evidence for the formation of crosslinked polydiacetylenes. IPNs of polydiacetylenes and an epoxy resin (diglycidyl ether of bisphenol A) were synthesized by using simultaneous and sequential methods of synthesis. A study of phase morphology of the simultaneous and sequential IPNs was carried out using electron microscopy, TMA, and DSC. 相似文献