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排序方式: 共有196条查询结果,搜索用时 15 毫秒
191.
Cotton FA Murillo CA Villagrán D Yu R 《Journal of the American Chemical Society》2006,128(10):3281-3290
Unprecedented strong electronic communication has been found in dimolybdenum pairs containing quadruply bonded Mo2(DAniF)3(+) (DAniF = N,N'-di-p-anisylformamidinate) units linked by dioxolene (C6X2O4(2-)) anions. The neutral compounds [Mo2(DAniF)3]2(C6X2O4) (1, X = H; 2, X = Cl; 3, X = NO2) and the singly oxidized products {[Mo2(DAniF)3]2(C6X2O4)Mo2}PF6 (4, X = H; 5, X = Cl) have been synthesized and characterized by X-ray crystallography and spectroscopic methods. Unusually short Mo-O distances (approximately 2.05 A for 1 and 2, and approximately 2.01 A for 4 and 5) are implicated in the remarkably strong interaction between [Mo2] units via the linkers. This leads to an extensive charge delocalization in the mixed-valence species, which is mediated by the dioxolene linker, as revealed by the large deltaE(1/2) values (763, 795, and 816 mV for 1, 2, and 3, respectively). Additional evidence for the strong electronic coupling is provided by UV-vis, NIR, and EPR spectroscopies and DFT calculations. 相似文献
192.
Martins A Marquardt U Kasravi N Alberico D Lautens M 《The Journal of organic chemistry》2006,71(13):4937-4942
The synthesis of a variety of alkylidene benzoxacycles via a domino palladium-catalyzed ortho-alkylation/intramolecular Heck reaction is described. Under the optimized conditions [Pd(OAc)2 (10 mol %), P(2-Furyl)3 (20 mol %), norbornene (4 equiv), Cs2CO3 (2 equiv), CH3CN, 80 degrees C], aryl iodides with oxygen-tethered Heck acceptors are coupled with alkyl bromides (5 equiv) to generate a variety of six- and seven-membered-ring benzoxacyclic products. 相似文献
193.
Dino R. Ferro Massimo Ragazzi Sergio Brückner Stefano V. Meille 《Macromolecular Symposia》1995,89(1):529-542
A computational approach to refine and analyze polymer crystal structures is presented, where both intra- and intermolecular interactions are simultaneously optimized by minimizing the total crystal potential energy in cartesian coordinates and utilizing a full-atom force field. The advantages of the present methodology are illustrated through several applications, including very recent results concerning the polymorphism of isotactic polypropylene. Some features of the computer program for molecular mechanics CHAMP, developed in our laboratory, are also described. 相似文献
194.
Incoronata Tritto Laura Boggioni Maria Carmela Sacchi Paolo Locatelli Dino R. Ferro Augusto Provasoli 《Macromolecular rapid communications》1999,20(5):279-283
A series of ethylene‐norbornene copolymers were synthesized in the presence of zirconocenes with different symmetries and ligand patterns and at different norbornene (N)/ethylene (E) mole ratios. Copolymers were characterized by 13C NMR spectroscopy; Inadequate NMR sequences were used also. The comparison of 13C NMR spectra of copolymers prepared with different norbornene content and the correlation between 13C NMR chemical shifts and conformational structures of the chain on the basis of molecular mechanics calculations were performed. Preliminary assignments were revised and new comonomer sequences such as ENNE which contain meso and racemo NN dyads were assigned. 相似文献
195.
Dino Ferri Dietmar Wolff Jürgen Springer Oriano Francescangeli Michele Laus Annino Sante Angeloni Giancarlo Galli Emo Chiellini 《Journal of Polymer Science.Polymer Physics》1998,36(1):21-29
The phase and orientational behaviors of a series of liquid crystalline (LC) AB-type diblock copolymers comprising thermotropic main-chain (MC) polyester and side-group (SG) polymethacrylate blocks were investigated by X-ray diffraction. The MC and SG blocks were phase separated and gave rise to their individual mesophases that coexisted at equilibrium. The samples were oriented by using either a magnetic field or a mechanical field. In magnetically aligned samples both the MC and SG microphases were oriented with their smectic planes orthogonal to the magnetic field direction, independent of the copolymer composition. Mechanically aligned, fiber samples showed different orientations of the MC and SG smectic planes for different sample compositions. In this case the disposition of the smectic planes of the MC and SG blocks was driven by the relative length of the two blocks. Some features of the X-ray patterns of the copolymers were compared to those of the MC and SG homopolymers. In addition, the MC smectic domains crystallized on annealing without affecting the orientation that had been achieved by applying a magnetic field. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 21–29, 1998 相似文献
196.
Incoronata Tritto Laura Boggioni Maria Carmela Sacchi Paolo Locatelli Dino R. Ferro 《Macromolecular Symposia》2004,213(1):109-122
Results of our studies on polymerization kinetics and tests of copolymerization statistical models of ethylene-norbornene (E-N) copolymers obtained on the basis of microstructures determined by 13C NMR analysis are reported. Ethylene-norbornene (E-N) copolymers were synthesized by catalytic systems composed of racemic isospecific metallocenes, i-Pr[(3Pri-Cp)(Flu)]ZrCl2 or a constrained geometry catalyst (CGC) and methylaluminoxane. Polymerization kinetics revealed that E-N copolymerization is quasi living under standard polymerization conditions. Calculations of the number of active sites and of chain propagation and chain transfer turnover frequencies indicate that the metal is mainly in the Mt-N* state, while the Mt-E* state contributes more to transfer and propagation rates. The first-order and the second-order Markov statistics have been tested by using the complete tetrad distribution obtained from 13C NMR analysis of copolymer microstructures. The root-mean-square deviations between experimental and calculated tetrads demonstrate that penultimate (second-order Markov) effects play a decisive role in E-N copolymerizations. Results show clues for more complex effects depending on the catalyst geometry in copolymers obtained at high N/E feed ratios. Comonomer concentration was shown to have a strong influence on copolymer microstructure and copolymer properties. The copolymer microstructure of alternating isotactic copolymers obtained with i-Pr[(3Pri-Cp)(Flu)]ZrCl2 have been described at pentad level. Second-order Markov statistics better describes also the microstrucure of these copolymers. 相似文献