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121.
The results of kinetic studies on ligand substitution in [M3(CO)11X]– complexes (M = Ru, Os; X = Cl, Br, I) are summarized. The [Os3(CO)11X]– complexes react with PPh3 under mild conditions to initially yield monosubstituted products [Os3(CO)10(PPh3)X]–. The rate of CO substitution obeys a first-order equation with respect to the concentration of the complex and does not depend on the ligand concentration. The rates of the reactions decrease in the order Cl > Br > I withH values increasing from 15 to 18 kcal mol–1 and S
values varying from –19 to –13 cal mol–1 K–1. The enhanced reactivities of these complexes as well as the low activation energies and negative activation entropies are discussed in terms of the effects of -X bridge formation on the transition state of the reaction. Reactions of PPN[Ru3(CO)11–x
(Cl)] (PPN is the bis(triphenylphosphine)iminium cation;x=0, 1) and PPN[Ru3(CO)9(3-I)] with alkynes are also reported. The reactivities of alkynes follow the order BuCCH PhCCH EtCCEt PhCCPh. The higher rates of the reactions of monosubstituted acetylenes compared with those of their disubstituted analogs are explained by agostic interaction between the metal atom and the C-H bond in the reaction transition state and by steric effects. The results obtained attest that the reaction with alkynes occursvia intermediates containing halide bridges and that 3-halide complexes are more reactive than 2-halide complexes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1540–1545, September, 1994.This work was supported by a Presidential Grant from Northwestern University. One of the authors (F. Basolo) wishes to thank Academician M. E. Vol'pin for the invitation to participate in the Workshop The Modern Problems of Organometallic Chemistry (INEOS-94) and Academician O. M. Nefedov for the invitation to publish a review in theRussian Chemical Bulletin. 相似文献
122.
The diffusion-limited reaction A+AA+B is studied in general dimension. The asymptotic decay of the system is found to depend nontrivially upon the initial concentration of A particles for certain ranges of the diffusion constant, backward reaction rate, and total concentration of particles. This nonequilibrium behavior is due to the formation of clusters centered about the initial A particles. A perturbative analysis ind=1 shows that the transition to the nonequilibrium dynamics is sharp and is quite similar to another previously studied reaction A+AA. Ford>1, a scaling argument is presented which describes the dependence of the asymptotic decay on the initial concentration of A particles and the equilibrium concentration for large backward reaction rates. Monte Carlo data are shown which confirm the analytic work ind=1, 2, and 3. 相似文献
123.
Limberg C 《Angewandte Chemie (International ed. in English)》2003,42(48):5932-5954
The oxo-functionalization of organic substrates with the aid of metal oxo moieties is of fundamental importance not only in nature but also in academic and industrial research. Nevertheless the corresponding reaction mechanisms remain among the most enigmatic in chemistry and few of them are understood in detail. Recent research efforts have resulted in significantly improved information: in the cases of many oxygenation reactions evidence has been provided for the occurrence radical intermediates, even though the high selectivity observed suggests to a different mechanism. Examples stem from various areas of chemistry and include processes involving molecular metal oxo complexes, gas-phase and matrix-isolated species, metalloenzymes, and solid-state oxide surfaces. This review treats this seemingly wide variety of systems with the aim of providing an overview of common reactivity patterns and principles, as well as open problems. 相似文献
124.
A study of the structural stability of clusters made up of a single component has been carried out within the Embedded Atom Method. Perfect icosahedral and cuboctahedral Cu, Ni, Pd, and Ag clusters with up to 5083 atoms have been compared. The icosahedron is found to be the stable structure for small clusters, and a change of structure from icosahedral to cuboctahedral is found as the cluster size increases. A contraction of the interatomic distances results when the cluster size decreases. 相似文献
125.
T.M. Tsai 《Journal of solid state chemistry》2004,177(10):3301-3309
MgO and Co1−xO powders in 9:1 and 1:9 molar ratio (denoted as M9C1 and M1C9, respectively) were sintered and homogenized at 1600°C followed by annealing at 850°C and 800°C, respectively to form defect clusters and precipitates. Analytical electron microscopic observations indicated the protoxide remained as rock salt structure with complicated planar diffraction contrast for M9C1 sample, however with spinel paracrystal precipitated from the M1C9 sample due to the assembly of charge- and volume-compensating defects of the 4:1 type, i.e., four octahedral vacant sites surrounding one Co3+-filled tetrahedral interstitial site. The spacing of such defect clusters is 4.5 times the lattice spacing of the average spinel structure of Mg-doped Co3−δO4, indicating a higher defect cluster concentration than undoped Co3−δO4. The {111} faulting of Mg-doped Co3−δO4/Co1−xO in the annealed M1C9 sample implies the possible presence of zinc blend-type defect clusters with cation vacancies assembled along oxygen close packed (111) plane. 相似文献
126.
127.
Complexes of azobisisobutyronitrile (AIBN) with titanium tetrachloride and vanadium tetrachloride have been synthesized and characterized. It was demonstrated that Ti(IV) and V(IV) form equimolar complexes with AIBN, with nitrile ligands located incis positions in the coordination spheres of metal atoms. Kinetics of thermal decomposition of free and complexed AIBN were studied and compared. The gas evolution rate was measured in the presence of tetrabutoxytitanium, which does not react with AIBN. It was demonstrated that complexing leads to a marked increase of the rate constant of AIBN thermal decomposition.Institute of Chemical Physics, Chernogolovka, Russian Academy of Sciences, 142432 Chernogolovka. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1746–1754, August, 1992. 相似文献
128.
Yu. E. Roginskaya F. Kh. Chibirova T. L. Kulova A. M. Skundin 《Russian Journal of Electrochemistry》2006,42(4):355-362
Products of lithium interaction with thin-film nanostructured SnO2-TiO2 (ST) oxides are studied with the aid of x-ray diffraction analysis and Moessbauer spectroscopy on the 119Sn nuclei. Electrochemical properties of a series of the ST electrodes with different concentrations of TiO2 varied from 0 to 20 mol % are also examined. It is concluded that the specific feature of the charge-discharge mechanism of the ST electrodes is a significant participation of oxygen in reversible reactions during insertion and extraction of lithium as compared with an alloying mechanism of operation of tin-containing anodes. The leading role in this is played by titanium oxide. Remaining stable towards reduction by lithium, it facilitates the holding of the neighboring layers of SnO2 in a nanodisperse state and in an oxidized state. The effect of a decrease in the capacity degradation in modified TiO2 electrodes, which is discovered in this work, is attributed to the hampering of the growth of nanocrystallites of β-Sn by interlayers of tin and titanium oxides mentioned above. 相似文献
129.
130.
Jens Hartig Andreas Schnepf L. Jos de Jongh David Bono Hansgeorg Schnöckel Prof. Dr. 《无机化学与普通化学杂志》2007,633(1):63-76
Towards the Understanding of the Unexpected Properties of the Metalloid Cluster Compound [Ga84(N(SiMe3)2)20][Li6Br2(THF)20]·2Toluol In several short communications we have recently reported on the electrical and superconducting properties of the crystalline title compound 1 which contains anionic Ga84R20‐moieties. Here we present a collection of these results, complemented and interpreted by using DFT‐calculations on model clusters (Ga84(NH2)20?). These calculations allow a) a first insight into the dynamics of the Ga84‐moieties (e.g. a rotation of the central Ga2‐dumbbell) and thus an explanation of the temperature‐dependent Ga‐NMR‐spectra described recently, and b) estimations on the lattice energy of 1 and its resulting unexpected energetic stabilization compared to metallic gallium. A possible contribution of the cations in the electrical conduction mechanism of 1 can also be made feasible with model calculations. The basis for all the results presented is to be found in the “perfect” arrangement of nanoscopic Ga84‐clusters in the crystal. This theoretically predicted condition for superconductivity in a “chain” of identical metal cluster molecules is a requirement which can hardly be realized by means of physical fabrication methods. Therefore, on the one hand the results presented here make for some disillusionment in the field of nanoscience, but on the other hand, especially in the field of synthetic chemistry, they present rewarding challenges for fundamental work in the future. 相似文献