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1.
The ion/molecule reactions of the molecular ion, the C3H ion, and the C3H ion obtained from 3-chloropropene. 1-bromopropene, 2-bromopropene, 3-bromopropene, bromocyclopropane. and 3-iodopropene have been studied with their neutral precursor in a Fourier-transform mass spectrometer (FT/ICR). The molecular ions react to yield primarily C6H except for the ion derived from 1-bromopropene that is unreactive. The kinetics of the 3-bromopropene molecular ion reveals that 18% of these ions must possess a different structure which is unreactive. The fact that C3H ions obtained from 2-bromopropene are the only ones to undergo proton transfer is taken as evidence that only this parent compound gives rise to 2-propenyl cations by low-energy electron impact. The C3H ions generated in these systems are shown to be roughly an equal mixture of propargylium ions that react to yield C6H and unreactive cyclopropenium ions.  相似文献   

2.
(E)-3α-Acetoxy-5, 10-seco-1(10)-cholesten-5-one ( 3 ) was synthesized by fragmentation of 3α-acetoxy-5α-cholestan-5-ol ( 1 ) using the photochemical version [3] of the lead tetraacetate reaction [4], and transformed into the corresponding 3-oxo-compound ( 5 ). Two conformations ( A and B ) were deduced for the 10-membered ring of 3 by analysis of the 1H- and 13C-NMR. spectra in toluene. The major conformation ( A ) corresponds to that found in the solid state by X-ray analysis. According to its NMR. spectra in toluene, the medium-sized ring of the diketone 5 exists also predominantly in two conformations, the major one being analogous to A (the solid-state conformation of the 3β-acetoxy isomer ( 9 ) [1]) and the minor one to A (see above). The stereochemistry of the acidcatalyzed and thermal cyclisations of 3 as well as of the corresponding 5-oxime is discussed in terms of conformational factors.  相似文献   

3.
Aqueous sols of TiO2 (anatase, particle radius 25 Å) were excited with (347.1 nm)-laser light and the reaction of valence-band holes with halide ions (X = I?, Br?, Cl?) was investigated. Hole transfer takes place within the duration of the (10 ns)-laser pulse and results in the formation of anion radicals according to the sequence: The quantum yield of X increases in the order Cl < Br < I, attaining 0.8 for I at pH 1. It is affected by pH, halide concentration and the presence of a protective agent for the sol. RuO2 deposited onto TiO2 enhances markedly Cl and Br -formation, but has no effect on the yield of I. Laser-photolysis investigation of halide oxidation were also carried out with colloidal Fe2O3 (particle radius 600 Å). For I2?formation, the quantum yield exceeds 0.9 indicating almost quantitative hole scavenging by iodide.  相似文献   

4.
Tetrammine-copper(II)-tetraiodide Cu(NH3)4I4 crystallizes in the monoclinic space group C 2/m. The crystal structure has been determined from X-ray diffractometer data and refined to Rw = 2.2%. Four coplanar nitrogen atoms and two axial iodine atoms form an octahedral coordination around Cu(II) with a pronounced 4 + 2 tetragonal distortion. A connection of the Cu(II) atoms by linear, centrosymmetric I polyiodide ions results in infinite chains of [Cu(NH3) I]-units. The central I-I-bond distance in I is 2.802(1) Å; a considerable amount of I-I bonding is indicated by the distance of 3.342(1) Å found for the terminal bonds. These intramolecular bond distances correspond to calculated I-I-bond orders of 0.80 and 0.43.  相似文献   

5.
63Cu-NMR.-Spectra of Cu(CH3CN)4X (X = ClO, BF, PF) and Cu(C5H5N)4X (X = ClO, BF) in solution are reported at different temperatures and concentrations. The influence of temperature on the linewidth and chemical shift indicates an equilibrium of Cu(CH3CN) and Cu(C5H5N) with another complex of lower symmetry. The preferential solvation of Cu (I) by pyridin in a mixture acetonitrile/pyridine is clearly shown.  相似文献   

6.
Superoxide ion apparently reacts with acidic substrates via species such as O2, HO2, O, HO and H2O2. Arylpyruvates give arylacetates and arylaldehydes indicating competing nucleophilic and free radical oxidation. Benzaldehyde is further oxidized by free radical and nucleophilic dioxygen species giving benzoic acid. p-Hydroxybenzaldehyde gives the corresponding benzoic acid which is best accounted for by HO2, since O and O2 are without effect. Hydroquinone is also produced presumably by nucleophilic attack of HO. Replacement of the acidic hydrogen atoms by sodium changes the product distribution in accord with these findings.  相似文献   

7.
The study at 25°C of the system K+? NH? CrO? SO? H2O has shown experimentally the existence of a new type of quaternary system of solubility with two cations and two anions. The solubility diagramm is caracterized by the presence of two adjacent ternary limiting systems with a miscibility gap, three univariant lines (one of them being evanescent), one invariant point, three binary and one ternary miscibility gaps.  相似文献   

8.
A most recently developed method to quantify the fragmentation pathways of excited radical cations is presented. Using bicyclobutane cation as an illustrative example, the RRKM analysis of the breakdown diagram determined by He-Iα photoelectron-photoion coincidence spectroscopy is outlined. The results imply complete isomerization to 1,3-butadiene cation preceding the dissociative processes. The rate-energy functions of four competitive primary fragmentation reactions, leading to C3H, C4H, C4H and C2H are established. There is compelling evidence that the production of C2H fragment ions does not compete effectively with these four reactions. The extent of kinetic and competitive shift effects is determined. The derived enthalpies of formation are in excellent accord with the available high quality reference data. The relative importance of different fragmentation pathways which ultimately lead to fragment ions of identical mass to charge ratio is assessed.  相似文献   

9.
The solubility of precipitated Cd(OH)2 was determined at 25°C in 1 M NaClO4, as a function of pH and of the ammonia content of the solutions. Formation constants were obtained for the following hydroxo, ammine and hydroxo-ammine complexes: CdOH+, Cd(OH)2, Cd(OH), CdNH, Cd(NH3), Cd(NH3), Cd(NH3) and Cd(OH)2NH3. The solubility product of the hydroxide was also calculated. The presence of polynuclear species was investigated by titrimetric determinations of the hydrogen ion concentration at constant metal concentration.  相似文献   

10.
The crystal structures of four anion cryptates [X? ? BT -6H+] formed by the protonated macrobicyclic receptor BT -6H+ with F?, Cl?, Br? and N have been determined. They provide a homogeneous series of anion coordination patterns with the same ligand. The small F?-ion is tetracoordinated, while Cl? and Br? are bound in an octahedron of H-bonds. The non-complementarity between these spherical anions and the ellipsoïdal cavity of BT -6H+ is reflected in ligand distortions. Structural complementarity is achieved for the linear triatomic substrate N, which is bound by two pyramidal arrays of three H-bonds, each interacting with a terminal N-atom of N. The formation constants of the complexes formed by BT -6H+ with a variety of anions (halides, N, NO, carboxylates, SO, HPO, AMP2?, ADP3?, ATP4?, P2O) have been determined. Very strong complexations are found, as well as marked electrostatic and structural effects on stability and selectivity; in particular the binding of F?, Cl?, Br?, and N may be analyzed in terms of the crystal structure data. The cryptand BT -6H+ is a molecular receptor containing an ellipsoïdal recognition site for linear triatomic substrates of size compatible with the size of the molecular cacity. Further developments of various aspects of anion coordination chemistry are considered.  相似文献   

11.
Using a new mathematical treatment, the nature and stability constants of the simple and mixed complex-species of copper(II) with hydroxyde and ammonia as ligands have been determined. The solubility curves of CuO in heterogeneous equilibrium have been identified in function of pH only and in function of pH and pNH3tot at 25° and unit ionic strength (NaClO4). The predominent species in the relatively dilute system limited by the ionic strength are [Cu2+], [Cu(OH)2], [Cu(OH)], [Cu(OH)], [Cu(NH3)], [Cu(NH3)], [Cu(NH3)], [Cu(NH3) (OH)+], [Cu(NH3)3(OH)+] and [Cu(NH3)2(OH)2].  相似文献   

12.
We describe a photochemical system for the generation of hydrogen by water reduction under visible light or sunlight irradiation of aqueous solutions containing the following components: a photosensitizer, the Ru (bipy) complex, for visible light absorption; a relay species, the Rh (bipy) complex, which mediates water reduction by intermediate storage of electrons via a reduced state; an electron donor, triethanolamine (TEOA) which provides the electrons for the reduction process and a redox catalyst, colloïdal platinum, which facilitates hydrogen formation. The conditions for efficient hydrogen production and the influence of the concentration of the components have been investigated; the metal complexes act as catalysts with high turnover numbers; excess bipyridine facilitates the reaction. The process contains two catalytic cycles: a ruthenium cycle and a rhodium cycle. The Ru cycle involves oxidative quenching of the *Ru(bipy) excited state by Rh(bipy) forming Ru(bipy) which is converted back to Ru(bipy) by oxidation of the electron donor TEOA, which is thus consumed. The Rh cycle comprises a complicated set of transformations of the initial Rh(bipy) complex. The reduced rhodium complex formed in the quenching process undergoes a series of transformations involving the Rh(bipy) complex and hydridorhodium-bipyridine species, from which hydrogen is generated by reaction with the protons of water. In view of the storage of two electrons in the reduced rhodium species, the process is formally a dielectronic water reduction. The properties and eventual participation of [Rh(III)(bipy)2LL′]n+(L,L′ = H2O, OH?) species are investigated. It is concluded that at neutral pH in presence of excess bipyridine, the cycle involving regeneration of the Rh(bipy) complex is predominant. A number of experiments have been performed with modified systems. Hydrogen evolution is observed with other photosensitizers (like proflavin), other relay species (like Rh(dimethylbipy) or Co(II)-bipyridine complexes), other donor species, or in absence of the platinum catalyst. It also occurs in absence of photosensitizer by sunlight of UV. irradiation of Rh(bipy) or by visible light irradiation of iridium (III)-bibyridine complexes. These systems deserve further investigations. The present photochemical hydrogen generating system represents the reductive component of a complete water splitting process. Its role in solar energy conversion and in photochemical fuel production is discussed.  相似文献   

13.
Reactivity-structure correlations for anisole and eleven of its substituted derivatives established from bromination rate constants in liquid SO2, unlike observations in water, show the reaction to be highly sensitive to substituent effects, (ρ = ?7.1; ρ = ?10.51). This result is ascribed to the solvation of the methoxy group which decreases the conjugation of para-substituted (ρ = ?9.70) compared to that of ortho-substituted derivatives (ρ = ?8.86). The highly solvated transition state lies far from reactants on the reaction coordinate and the positive charge developed in this state is nearly unity.  相似文献   

14.
The n ionization energies I and the gas-phase basicities GB of CH3-, Cl-, or CN-substituted quinuclidines have been measured by PE and ICR spectroscopy. The dependence of the shifts ΔI and ΔGB (relative to the values of the parent molecule) allow conclusions about the charge dispersal accompanying the n ionization or the protonation of quinuclidine in the gas phase. The agreement with the results of a minimal basis set ab initio calculation is excellent. Comparison of the solution pKa values with either I or GB reveals that 2-substituted quinuclidines exhibit sizeable solvent-induced proximity effects, i.e. that the corresponding quinuclidinium ions are more acidic in solution than expected on the basis of the gas-phase basicities. This agrees with earlier results concerning 2-substituted pyridines.  相似文献   

15.
The crystal structures of Mn5O8 and Cd2Mn3O8 are determined from single crystal and high resolution X-ray powder data. Both structures have very similar monoclinic unit cells, space group CC2/m, and are isotypic: Hence, the true formula of Mn5O8 is MnMnO8. The crystal structure consists of pseudohexagonal MnIV sheets (bc) with similar oxygen sheets on either side, giving a distorted octahedral coordination to the MnIV. As every fourth MnIV is missing in these “main layers”, their composition becomes Mn3O8, and chains of coordination octahedra linked by common edges become distinct. Above and below the empty MnIV sites are either MnII or CdII completing the composition MnMnO8 or Cd2Mn3O8 respectively. Examples of similar “double layer” structures are given.  相似文献   

16.
Recrystallization of Cs3P7 from liquid NH3 yields the triammoniate Cs3P7·3 NH3, which loses the weakly bound NH3 of crystallization below 253 K. A low-temperature crystal-structure analysis shows that Cs3P7· NH3 consists of a framework of heptaphosphanortricyclane anions P and Cs+ cations with NH3 molecules completing the coordination of the cations. The framework is built from Cs3P7 layers connected by only few Cs…?P interactions, the interlayer gap being filled by a two-dimensional network of NH3. The Cs7P7 part of the structure completes a family of alkali-metal-polyphosphide substructures which range from [RbP7]2? or [CsP11]2? chains over [Cs2Pn]? layers (n = 7, 11) to now [Cs3P7] frameworks.  相似文献   

17.
The Influence of Aniline pK Values on the Formation and Reactivity of Substituted Butadienes from Methyl Coumalate The product of the reaction between 2 equiv. of methyl coumalate ( 1 ) and 1 equiv. of a substituted aromatic amine depends on the pK value of the latter. Aromatic amines with pK values between 1.05 and 2.8 produce bicyclic lactones 4 , whereas those with higher pK values also give 2-azabicyclo[3.3.1]nona-3,7-diene-9-carboxylic acids 9 . The latter, products of the intramolecular Diels-Alder reaction 8 → 9 , may in certain cases even prevail.  相似文献   

18.
The ternary Cu2+?2,2′-bipyridyl-adenosine-5′-monophosphate-N(1)-oxide complex was investigated and compared with the binary Cu2+-adenosine-5′-monophosphate-N(1)-oxide complex (I) (cf. [2]). In both complexes Cu2+ is bound to the o-amino-N-oxide group of adenosine-5′-monophosphate-N(1)-oxide (HL). The stabilities of the complexes monoprotonated at the phosphate group are of the same order: log K = 11,20, and log K = 11,19. The acidity constants for the deprolonation of the phosphate group in these complexes are slightly different (pK = 5,55, and pK = 5,88), but as expected both values are lower than the corresponding value pK = 6,12 of the ligand.  相似文献   

19.
The linear free energy relationship of Sicher for relative reactivity towards chromic acid oxidation (ΔΔG) as a function of thermodynamic stability (ΔG) has been reexamined with 23 pairs of epimeric alcohols. The plot of ΔG vs. ΔG has a slope of 0.8, a correlation coefficient of 0.97 and a standard deviation of 0.23 kcal/mol on ΔΔGOx. The limitations of the relationship and the exceptions are discussed.  相似文献   

20.
The kinetics of formation and dissociation of [V(H2O)5NCS]2+ have been studied, as a function of excess metal-ion concentration, temperature, and pressure, by the stopped-flow technique. The thermodynamic stability of the complex was also determined spectrophotometrically. The kinetic and equilibrium data were submitted to a combined analysis. The rate constants and activation parameters for the formation (f) and dissociation (r) of the complex are: k/M ?1 · S?1 = 126.4, k/s?1 = 0.82; ΔH /kJ · mol?1 = 49.1, ΔH/kJ · mol?1 = 60.6; ΔS/ J·K?1·mol?1= ?39.8, ΔSJ·K?1·mol?1 = ?43.4; ΔV/cm3·mol?1 = ?9.4, and ΔV/cm3 · mol?1 =?17.9. The equilibrium constant for the formation of the monoisothiocynato complex is K298/M ?1 = 152.9, and the enthalpy and entropy of reaction are ΔH0/kJ · mol?1 = ? 11.4 and ΔS0/J. K?1mol?1 = +3.6. The reaction volume is ΔV0/cm3· mol?1 = +8.5. The activation parameters for the complex-formation step are similar to those for the water exchange on [V(H2O)6]3+ obtained previously by NMR techniques. The activation volumes for the two processes are consistent with an associative interchange, Ia, mechanism.  相似文献   

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