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41.
The coordination chemistry of amine tris(phenolate) ligands around V(III) and V(V) is described for the first time. Three amine tris(phenolate) ligands were employed featuring different steric and electronic influence exerted by the phenolate substituents in the ortho and para positions being either t-Bu, Me, or Cl. V(III) complexes of all ligands (1-3) were readily obtained by reaction between the ligand precursors and VCl3(THF)3 in the presence of triethylamine. The complexes obtained were pentacoordinate, a THF ligand completing the coordination sphere of the metal, which was found to be of almost perfect TBP geometry, as revealed by crystallography. V(V) oxo complexes of all the ligands (4-6) were readily obtained by a reaction between the ligand precursors and VO(OPr)3. The oxo complexes of the alkyl-bearing ligands (4 and 5) could also be synthesized by the air oxidation of the corresponding V(III) complexes (1 and 2); however, the attempted air oxidation of the V(III) complex bound to the electron-poor ligand (3) did not yield the corresponding oxo complex 6. 1H NMR and crystallographic analysis of complexes 4 and 5 supported their TBP structures. Complex 6, on the other hand, was found to be composed of a TBP complex (6a) and an octahedral complex (6b) in equilibrium, the octahedral complex being more stable at lower temperatures. An X-ray structure of 6b revealed a mononuclear oxo complex, the sixth coordination site being occupied by an aqua ligand to which two THF molecules are H-bonded. Complexes 4-6 catalyze the epoxidation of olefins by t-BuOOH, albeit slowly. These complexes may thus be considered as structural and functional models of vanadium-dependent haloperoxidase enzymes. 相似文献
42.
Amos Korin Moshe Levy David Vofsi 《Journal of polymer science. Part A, Polymer chemistry》1980,18(1):109-121
Vinyl fluoride was polymerized by photochemical initiation in a continuous-flow cylindrical reactor at room temperature and at pressures of up to 30 atm. Copolymers with vinyl acetate were prepared in order to improve the solubility and processability of poly(vinyl fluoride) (PVF). The copolymers were hydrolyzed to the corresponding vinyl alcohol copolymers and yielded hydrophilic films that are strong and flexible only when swollen by water. It was found that on hydrolysis the Tg, Tm, and heat of fusion as well as degree of crystallinity increased. It was suggested that PVF and the copolymers with vinyl alcohol are isomorphous. 相似文献
43.
LetK be a local field,T the maximal tamely ramified extension ofK, F the fixed field inK
sof the Frattini subgroup ofG(K), andJ the compositum of all minimal Galois extensions ofK containingT. The main result of the paper is thatF=J. IfK is a global field andK
solv is the maximal prosolvable extension ofK, then the Frattini group of
% MathType!End!2!1!(K
solv/K) is trivial.
Partially supported by a grant from the G.I.F., the German-Israeli Foundation for Scientific Research and Development. 相似文献
44.
45.
Yoel Tsur Harold H. Levine Moshe Levy 《Journal of polymer science. Part A, Polymer chemistry》1974,12(7):1515-1529
Polybenzimidazoles were prepared in poly(phosphoric acid) from isophthalic, m- and p-phenylene diacetic, succinic, adipic, suberic, and sebacic acids and 3,3′-diaminobenzidine, 3,3′,4,4′-tetraaminodiphenyl ether and 3,3′,4,4′-tetraaminodiphenylmethane. The thermal, mechanical, and bonding properties were studied. A 3:1 copolymer of isophthalic and m-phenylenediacetic acid with 3,3′-diaminobenzidine showed the best results as far as isothermal oxidation resistance and thermal and processing characteristics. 相似文献
46.
Several chiral octahedral complexes of the general formula [Ru(bpy)2 (Lig)][PF6]2 (Lig = a ligand that can participate in pi-stacking interactions such as eilatin, isoeilatin, and tpphz) were synthesized in both the racemic and enantiomerically pure/enriched forms. Nonracemic mixtures of enantiomers of all these complexes exhibit splitting of the 1H NMR spectra (NMR nonequivalence); i.e., each spectrum contains a major and a minor set of peaks. The origin of this phenomenon is attributed to a fast equilibrium between monomers and discrete dimers held together by pi-stacking interactions, and it is observed for a wide range of pi-stacking interaction strengths. The NMR spectrum splitting exhibited by these complexes can be exploited for the evaluation of their enantiomeric excess simply from the integral ratio, without addition of chiral shift reagents. 相似文献
47.
Gerbasi D Brumer P Thanopulos I Kral P Shapiro M 《The Journal of chemical physics》2004,120(24):11557-11563
An application of a recently proposed [P. Kral et al., Phys. Rev. Lett. 90, 033001 (2003)] two step optical control scenario to the purification of a racemic mixture of 1,3 dimethylallene is presented. Both steps combine adiabatic and diabatic passage phenomena. In the first step, three laser pulses of mutually perpendicular linear polarizations, applied in a "cyclic adiabatic passage" scheme, are shown to be able to distinguish between the L and D enantiomers due to their difference in matter-radiation phase. In the second step, which immediately follows the first, a sequence of pulses is used to convert one enantiomer to its mirror-imaged form. This scenario, which only negligibly populates the first excited electronic state, proves extremely useful for systems such as dimethylallene, which can suffer losses from dissociation and internal conversion upon electronic excitation. We computationally observe conversion of a racemic mixture of dimethylallene to a sample containing approximately 95% of the enantiomer of choice. 相似文献
48.
We derive a closed-form result for the leading thermal contributions which appear in the n-dimensional ? 3 theory at high temperature. These contributions become local only in the long wavelength and in the static limits, being given by different expressions in these two limits. 相似文献
49.
Abstract We report the observation of an optically isotropic phase in the new disc-like mesogen 2,3,7,8,12,13-hexa(octadecanoyloxy)truxene. On cooling, this optically isotropic phase goes over into a nematic phase, while on heating a columnar phase grows in. To our knowledge this is the first example of a pure discotic mesogen exhibiting an isotropic phase below the temperature existence of a columnar phase. Our findings are supported by refractive index measurements of this compound as a function of temperature. 相似文献
50.
Yevgeniy Frenkel Andrew J. Majda Boualem Khouider 《Theoretical and Computational Fluid Dynamics》2013,27(3-4):533-559
This paper presents a study of the diurnal cycle of tropical precipitation and its interaction with convectively coupled waves in the context of simple models with crude vertical resolution. One and two baroclinic mode models are tested in both the context of a one-column model and the context of a full spatial dependency that permits waves to propagate and interact with the diurnal cycle. It is found that a one baroclinic mode model is capable of reproducing a realistic diurnal cycle of tropical precipitation both over land and over the ocean provided an adequate switch function is used to mimic the congestus preconditioning mechanism that operates in the multicloud model of Khouider and Majda. However, a full two baroclinic mode multicloud model is needed to capture the interaction of convectively coupled tropical waves with the diurnal cycle. In a more conventional mass flux parameterization framework, both one and two baroclinic mode models fail to capture the diurnal cycle of tropical precipitation. 相似文献