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81.
The phenomenon of agostic interactions is reviewed and the nature of the interaction is revisited. A historical perspective is followed by an overview of experimental techniques used to diagnose agostic behavior, and previous interpretations of agostic bonding are presented. A series of simple metal alkyl complexes is considered and a new model for the phenomenon in d(0) systems is developed which sets them apart from agostic late-transition-metal complexes. Factors such as the valence electron count and coordination number of the metal center are revealed to be unimportant in facilitating the interaction in most d(0) systems. The charge density distribution in several transition-metal alkyl complexes is explored by experimental and theoretical techniques, including the powerful "Atoms in Molecules" approach. Local charge concentrations are shown to play an important role in the agostic interaction. Finally, we demonstrate for the first time a way to manipulate and control the magnitude and disposition of such local charge concentrations, and hence the strength of agostic interactions in d(0) metal alkyl complexes. 相似文献
82.
Enn?LustEmail author Alar?J?nes Tanel?P?rn Priit?Nigu 《Journal of Solid State Electrochemistry》2004,8(4):224-237
Electrochemical characteristics for the nanoporous carbon|Et4NBF4+acetonitrile interface have been studied by cyclic voltammetry and impedance spectroscopy methods. The influence of the electrolyte concentration and thickness of the nanoporous electrode material on the shape of the cyclic voltammetry and impedance curves has been established and the reasons for these phenomena are discussed. A value of zero charge potential, depending slightly on the structure and concentration of the electrolyte, the region of ideal polarizability and other characteristics have been established. The nanoporous nature of the carbon electrodes introduces a distribution of resistive and capacitive elements, giving rise to complicated electrochemical behaviour. Analysis of the complex plane plots shows that the nanoporous carbon|Et4NBF4+acetonitrile electrolyte interface can be simulated by an equivalent circuit, in which two parallel conduction paths in the solid and liquid phases are interconnected by the double-layer capacitance in parallel with the complex admittance of the hindered reaction of the charge transfer or of the partial charge transfer (i.e. adsorption stage limited) process. The values of the characteristic frequency depend on the electrolyte concentration and electrode potential, i.e. on the nature of the ions adsorbed at the surface of the nanoporous carbon electrode. The value of the solid state phase resistance established is independent of the thickness of the electrode material. 相似文献
83.
At sufficiently high concentrations of methanol and of alkali salts in aqueous silica dispersions, the negative -potentials of the particles are decreased. This effect is more pronounced with lithium than with other alkali cations, and it is independent on the anion. The NMR spectra indicate lithium adsorption on silica from mixed solvents, but not in the absence of alcohol.Supported by a contract with the XMX Corporation, Burlington, Massachusetts, USA 相似文献
84.
The conformal charge is an important quantity which characterizes the nature of the two-dimensional phase transition. We report a first attempt to use a new numerical method to calculate the conformal charge. In this paper, we apply our method to the 2-dimensional,
4, continuous-spin Ising model. By varying the parameters in the Hamiltonian, one can change continuously from the known Gaussian limit to the Ising limit. It is well known that the critical points for these two systems are not in the same universality class. We study this behavior for the Gaussian model, the single-well 4 model, the border model, and the double-well
4 model for a large lattice. Our results, while giving a good general picture, are not so far sufficient to differentiate whether the non-Gaussian cases studied belong to the Ising model universality class or not. Further studies of other lattice sizes should serve to improve greatly our conclusions. 相似文献
85.
A series of “push-pull” porphyrins with 4-nitrophenyl and 4-aminophenyl substituents were synthesized and separated by flash column chromatographic techniques. They were fully characterized by elemental analysis, FAB-MS, FTIR, UV-visible, and 1H NMR spectroscopies. The unsymmetrical π-electron distribution of the porphyrins caused by the donor (amino) and acceptor (nitro) substituents were investigated by 1H NMR technique. The pyrrole-H resonance positions can be correlated to the Hammett σ constants of the substituents. Although with strong donor and acceptor substituents, UV-visible spectra show the push-pull porphyrins have rather weak solvatochromism and hence limited intramolecular charge-transfer character. 相似文献
86.
The influence of the surfactant charge on micellization was studied on sodium n-dodecane-phosphonates, varying the charge of the surfactant ion from 0 to 2. The effects on the cmc, hydrolysis, micelle
composition, and micelle ionization degree were studied. The increase of one e unit in the charge of the surfactant species reduces the cmc by about one order of magnitude.
Received: 18 November 1996 Accepted: 5 March 1997 相似文献
87.
Michael Chariss Andrea Zickgraf Heike Stenger Elmar Bru Cristelle Desmarquet Martin Drger Silke Gerstmann Dainis Dakternieks James Hook 《Polyhedron》1998,17(25-26)
44 members of thecompound series Ph4−nMRn (M=Si, Ge, Sn, Pb; R=o-, m-, p-Tol; n=0–4) were synthesized (15 newcompounds). The crystal structures of Ph3Sn (o-Tol) and PhSn (o-Tol)3 were determined and compared to 16 known structures. Subject to the distanced (M–C), an interplay between through-space π–π repulsion and π–σ attraction leads to either elongated or compressed tetrahedral geometry. 29 Si-, 119 Sn- and 207 Pb-NMR chemical shifts were determined in solution and in the solid state. 73 Ge chemical shifts were measured only in solution. Anupfield or downfield sagging of the chemical shifts along each series is rationalized in terms of a π–σcharge transfer which is constrained by torsion of the aromatic groups. 相似文献
88.
Keita Hamasaki Asao Nakamura Akihiko Ueno Fujio Toda 《Journal of inclusion phenomena and macrocyclic chemistry》1992,13(4):349-359
The effects of -cyclodextrin (-CyD), heptakis(2,6-di-O-methyl)--cyclodextrin (DMCyD) and heptakis(2,3,6-tri-O-methyl)--cyclodextrin (TMCyD) ontrans-cis photoisomerization of 1-ethyl-4-(4-hydroxystyryl)pyridinium (POH) have been studied in aqueous solutions. The ratio of [cis]/[trans] for POH in the photostationary state at pH 8.54 was remarkably reduced by the presence of CyD or DMCyD. The reduction of the [cis]/[trans] ratio in the photostationary state was explained in terms of the shift of the equilibrium of POH
+
trans
PO
trans
+ H– toward PO
trans
formation. The binding constants of CyD and DMCyD for PO
trans
were 2.00- and 1.36-fold larger than those for POH
+
trans
, respectively. The binding constants of TMCyD for both species are much smaller than those of CyD and DMCyD. This result indicates that PO
trans
, which has a betain structure, forms stable complexes with CyD and DMCyD with its hydrophobic parts inside and the charged parts outside the CyD cavities. 相似文献
89.
To evaluate the reactivity of new difluroroaromatic compounds in nucleophilic substitution, the positive charges on carbon
atoms of C−F bonds were calculated using the quantum-chemical semiempirical PM3 method. A correlation between the charges
calculated and the chemical shifts in the19F NMR spectra was established.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 623–625, April, 1998. 相似文献
90.
纳米碳纤维负载钯催化剂在Heck反应中的应用——载体相互作用的影响 总被引:1,自引:0,他引:1
使用多元醇还原法制备了均匀分散的钯纳米颗粒.将钯纳米颗粒负载于板式、鱼骨式和管式纳米碳纤维,得到稳定、可重复使用的非均相催化剂.实验结果表明,钯纳米胶粒同载体之间的电位差对钯在载体上的负载量、粒子大小以及Heck反应中钯的溶失量有很大的影响.在制备过程中,增加钯纳米胶粒同纳米碳纤维表面的电位差能够大大降低钯在Heck反应中的流失.催化剂的反应活性随钯粒子的增大而降低. 相似文献