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491.
Jabri A Temple C Crewdson P Gambarotta S Korobkov I Duchateau R 《Journal of the American Chemical Society》2006,128(28):9238-9247
The reaction of the highly selective [CySCH2CH2N(H)CH2CH2SCy]CrCl3 catalyst precursor with alkyl aluminum activators was examined with the aim of isolating reactive intermediates. Reaction with Me3Al afforded a cationic trivalent chromium alkyl species {[CySCH2CH2N(H)CH2CH2SCy]CrMe(mu-Cl)}2{(AlMe3)2(m-Cl}2.(C7H8)2 (1a). Although it was not possible to obtain crystalline samples of sufficient quality from the reaction with MAO (the most preferred activator), the near-to-identical EPR spectra indicated a very close structural similarity with 1a. Ethylene oligomerization tests clearly revealed that 1 and other cationic trivalent dimeric complexes {[CySCH2CH2N(H)CH2CH2SCy] CrCl(mu-Cl)}2{AlCl4}2.(C7H8)1.5 (2), monomeric [(CySCH2CH2N(H)CH2CH2SCy)CrCl2 (THF)][AlCl4] (3), and {[CySCH2CH2N(H)CH2CH2SCy]Cr(eta2-AlCl4)}{Al2Cl7} (4) adducts display the same catalyst selectivity as the [CySCH2CH2N(H)CH2CH2SCy]CrCl3 complex and, therefore, are probably all precursors to the same catalytically active species. 2, 3, and 4 were obtained upon treatment of [CySCH2CH2N(H)CH2CH2SCy] CrCl3 with different stoichiometric ratios of AlCl3.. When i-BAO activator was used, reduction of the metal center occurred readily, affording {([CySCH2CH2N(H)CH2CH2S Cy]Cr)(mu-Cl)]2}{(i-Bu)2AlCl2}2 (5). 5 is also a selective catalyst, thus indicating that trivalent species are most probably precursors to a divalent catalytically active complex. Reaction of CrCl2(THF)2 with the ligand afforded the labile divalent adduct [CySCH2CH2N(H)CH2CH2SCy]CrCl2(THF) (6), also catalytically active and selective. Instead, deprotonation of the ligand with n-BuLi followed by reaction with CrCl2(THF)2 gave the dinuclear complex [(mu-CySCH2CH2NCH2CH2SCy)CrCl]2 (7), which did not produce oligomers. 相似文献
492.
Casey CP Bikzhanova GA Cui Q Guzei IA 《Journal of the American Chemical Society》2005,127(40):14062-14071
Reduction of imines by [2,5-Ph2-3,4-Tol2(eta(5)-C4COH)]Ru(CO)2H (2) produces kinetically stable ruthenium amine complexes. Reduction of an imine by 2 in the presence of an external amine trap gives only the complex of the newly generated amine. Reaction of 2 with H2N-p-C6H4N=CHPh (11), which contains an intramolecular amine trap, gave a 1:1 mixture of [2,5-Ph2-3,4-Tol2(eta(4)-C4CO)](CO)2RuNH(CH2Ph)(C6H4-p-NH2) (8), formed by coordination of the newly generated amine to the ruthenium center, and [2,5-Ph2-3,4-Tol2(eta(4)-C4CO)](CO)2RuNH2C6H4-p-NHCH2Ph (9), formed by coordination of the amine already present in the substrate. These results require transfer of hydrogen to the imine outside the coordination sphere of the metal to give a coordinatively unsaturated intermediate that can be trapped inside the initial solvent cage. Amine diffusion from the solvent cage must be much slower than coordination to the metal center. Mechanisms requiring prior coordination of the substrate to ruthenium would have led only to 8 and can be eliminated. 相似文献
493.
Reduction of the two trivalent 2,6-{[2,6-(i-Pr)2C6H5]N=C(CH3)}2(C5H3N)VCl3 and {[2,6-{[2,6-(i-Pr)2C6H3]N-C=(CH2)}2(C5H3N)]VCl(THF) complexes with excess NaH afforded two corresponding end-on dinitrogen-bridged complexes [2,6-{[2,6-(i-Pr)2C6H5]N=C(CH3)}2(C5H3N)V]2(m-N2).(hexane) (1) and [{[2,6-{[2,6-(i-Pr)2C6H3]N-C=(CH2)}2(C5H3N)]V]2(m-N2).(hexane) (3). Despite their very close structural similarity, the two species have completely different natures. The first is paramagnetic and may be regarded as generated by the two-electron attack of two formally zerovalent vanadium moieties on the same N2 unit. In the nearly diamagnetic 3 instead, the N2 unit has been reduced by two vanadium atoms, formally divalent. Structural analysis and DFT calculations have indicated that partial reduction of the bridging nitrogen occurred for both complexes while, in the case of 1, substantial metal-to-ligand electron transfer also occurs. 相似文献
494.
Burns CA Giura P Said A Shukla A Vankó G Tuel-Benckendorf M Isaacs ED Platzman PM 《Physical review letters》2002,89(23):236404
Inelastic x-ray scattering was used to measure the plasmon as a function of electron density in liquid lithium ammonia as well as the low temperature solid phase. As the electronic density is lowered, electronic correlation effects cause the random-phase approximation (RPA) to break down, requiring more advanced theoretical treatments. The deviation from RPA becomes greatest at the lowest electronic densities. We also see evidence for decreased electronic screening as shown by an increase in the strength of the pseudopotential at lower concentrations. Plasmon behavior in the solid is similar to that of the heavier alkali metals, but surprisingly different than in the liquid. 相似文献
495.
Biaryl lactones were prepared by novel domino retro-Michael-aldol-lactonization reactions of 2,3-dihydropyrans. 相似文献
496.
The nature of small ions in electrolytic (e.g., aqueous) solutions is discussed in terms of the configuration of the adjoining polarized medium, and the role of this configuration in electronic transitions involving one or a pair of ions is treated in a general way. Light absorption by a single ion is shown to depend critically on this configuration; a theory developed previously by the authors is reviewed, and future possibilities of exploring the nature of the configuration by investigation of such spectra are explained. Electronic transitions, such as an “electron transfer” process, during binary collisions of ions are treated, and a general method is developed, based uponDebye's “diffusion” theory for ion collision rates and a nonadiabatic type of potential curve. Rates of chemical processes are found to depend decisively on the interaction of two ions at separations where the simple coulomb law is not valid. 相似文献
497.
Miroslav?Ilia?Email author Vladimír?Kell? Timo?Fleig Miroslav?Urban 《Theoretical chemistry accounts》2003,110(3):176-184
The electric dipole moment and the static dipole polarizability of the hydrogen iodide molecule were studied using sophisticated correlated and relativistic methods. Both scalar and spin–orbit relativistic effects were carefully accounted for. We conclude that the large differences between the theoretical and experimental dipole moment, the dipole moment derivative and the polarizability cannot be reconciled by improved account of electron correlation and relativistic effects. The most striking difference between theory and experiment is observed for the polarizability anisotropy. We believe that experimental data, namely the experimental dipole moment (the most recent value is 0.176 au as compared to our best theoretical estimate, 0.154±0.003 au), the parallel polarizability (44.4 and 38.47±0.05 au) and the anisotropy (11.4 and 2.33±0.05 au) must be inaccurate. Experimental and theoretical perpendicular polarizability components (33.0 and 36.14±0.05 au,) and the mean polarizability (36.8 and 36.92±0.05 au) agree better. Our vibrationally corrected relativistic CCSD(T) results represent the most sophisticated predictions of electric properties of HI obtained so far.Contribution to the Björn Roos Honorary Issue 相似文献
498.
499.
We introduce a class of combinatorial hypersurfaces in the complex projective space. They are submanifolds of codimension
2 inℂP
n
and are topologically “glued” out of algebraic hypersurfaces in (ℂ*)
n
. Our construction can be viewed as a version of the Viro gluing theorem relating topology of algebraic hypersurfaces to the
combinatorics of subdivisions of convex lattice polytopes. If a subdivision is convex, then according to the Viro theorem
a combinatorial hypersurface is isotopic to an algebraic one. We study combinatorial hypersurfaces resulting from non-convex
subdivisions of convex polytopes, show that they are almost complex varieties, and in the real case, they satisfy the same
topological restrictions (congruences, inequalities etc.) as real algebraic hypersurfaces.
A part of the present work was done during the stay of the second author at the Fields Institute, Toronto, and at the NSF
Science and Technology Research Center for the Computation and Visualization of Geometric Structures, funded by NSF/DMS89-20161.
The work was completed during the stay of both authors at Max-Planck-Institu für Mathematik. The authors thank these funds
and institutions for hospitality and financial support. 相似文献
500.
We estimate the interval where the distance distribution of a code of length n and of given dual distance is upperbounded
by the binomial distribution. The binomial upper bound is shown to be sharp in this range in the sense that for every subinterval
of size about √n ln n there exists a spectrum component asymptotically achieving the binomial bound. For self-dual codes we
give a better estimate for the interval of binomiality. 相似文献