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31.
Syntheses and Crystal Structures of the Phosphaneimine Complexes MCl2(Me3SiNPMe3)2 with M = Zn and Co, and CoCl2(HNPMe3)2 The molecular complexes MCl2(Me3SiNPMe3)2 (M = Zn, Co) have been prepared by the reaction of the dichlorides of zinc and cobalt with Me3SiNPMe3 in CH3CN and CH2Cl2, respectively, whereas the complex CoCl2(HNPMe3)2 has been prepared by the reaction of CoCl2 with NaF in boiling acetonitrile in the presence of Me3SiNPMe3. All complexes were characterized by IR spectroscopy and by crystal structure determinations. The complexes MCl2(Me3SiNPMe3)2 crystallize isotypically. ZnCl2(Me3SiNPMe3)2: Space group P212121, Z = 4, 2677 observed unique reflections, R = 0.024. Lattice dimensions at ?70°C: a = 1243.6; b = 1319.0; c = 1464.7 pm. CoCl2(Me3SiNPMe3)2: Space group P212121, Z = 4, 3963 observed unique reflections, R = 0,071. Lattice dimensions at ?80°C: a = 1236.3; b = 1317.4; c = 1457.6 pm. CoCl2(HNPMe3)2 · CH2Cl2: Space group Pbca, Z = 8, 1354 observed unique reflections, R = 0.055. Lattice dimensions at ?80°C: a = 1247.3; b = 998.4; c = 2882.4 pm. All complexes have monomeric molecular structures, in which the metal atoms are coordinated in a distorted tetrahedral fashion by the two chlorine atoms and by the nitrogen atoms of the phosphaneimine molecules.  相似文献   
32.
Chlorothionitrene Complexes of Tungsten. Crystal Structure of [WCl4(NSCl)]2 Tungsten hexachloride reacts with trithiazyl chloride, (NSCl)3, yielding the chlorothionitrene complex [WCl4(NSCl)]2, from which AsPh4[WCl5(NSCl)] can be obtained by reaction with AsPh4Cl. Both complexes are characterized by their i.r. spectra. The crystal structure of [WCl4(NSCl)]2 was determined and refined with X-ray diffraction data (1059 reflexes, R = 0.055). It crystallizes in the monoclinic space group P21/n with the lattice constants a = 1523, b = 904, c = 583 pm and β = 91.35°. In the unit cell there are two centrosymmetric [WCl4(NSCl)]2 molecules in which the W atoms are linked via two chloro bridges; short and long W? Cl distances (244 and 265 pm) alternate in the W2Cl2 ring, the NSCl groups are found in the trans positions to the longer W? Cl bonds. The WNS bond angle (175°) and short bond distances correspond to a formulation .  相似文献   
33.
A new phase CrTe3 was discovered and its existence was confirmed by differential thermal analysis and X-ray investigations. Symmetry and lattice parameters as well as the temperature of its peritectic decomposition were determined.
Über die PhaseCrTe 3
Zusammenfassung Eine neue Phase CrTe3 wurde entdeckt und ihre Existenz wurde mittels differential-thermoanalytischer und röntgenographischer Untersuchungen sichergestellt. Es wurden Symmetrie und Gitterparameter sowie auch die Temperatur des peritektischen Zerfalls bestimmt.
  相似文献   
34.
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 RuE 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-η66-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   
35.
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   
36.
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   
37.
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   
38.
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   
39.
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   
40.
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   
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