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51.
The study on coordination copolymerization of styrene (S) with maleic anhydride (MA) by rare-earth coordination catalysts, NdL_3-Al(i-Bu)_3, has been successfully carried out for the first time. Some features, kinetic behavior, and mechanism of the SMA copolymerization by Nd(naph)_3-Al(i-Bu)_3 system are described and discussed. The copolymex of styrenemaleic anhydride prepared by the NdL_3-Al(i-Bu)_3 systems in benzene at 50℃ is an alternating-rich white powder having high number-average molecular weight of 6—8.5×10~5. The overall activation energy for the polymerization was found to be 10.5KJ/mol. The polymerization was not suppressed by addition of hydroquinone. The catalytic activity of various ligands in NdL_3 for the copolymerization decreases in the following order: Nd (naph)_3>Nd-(P_(507))_3~NdCl_3-6H_2O>Nd(P_(204))_3>Nd(acac)_3. 3H_2O. The experimental results are explained based on a mechanism to be the coordination-type copolymerization in terms of the participation of a monomer-monomer c 相似文献
52.
本文概述了配位聚合载体化催化剂的ESR研究进展,介绍了载体研究、活性中心研究及计算机模拟技术研究方面的发展概况. 相似文献
53.
Zou JW Jiang YJ Guo M Hu GX Zhang B Liu HC Yu QS 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):740-751
Ab initio calculations have been performed on a series of complexes formed between halogen-containing molecules and ammonia to gain a deeper insight into the nature of halogen bonding. It appears that the dihalogen molecules form the strongest halogen-bonded complexes with ammonia, followed by HOX; the charge-transfer-type contribution has been demonstrated to dominate the halogen bonding in these complexes. For the complexes involving carbon-bound halogen molecules, our calculations clearly indicate that electrostatic interactions are mainly responsible for their binding energies. Whereas the halogen-bond strength is significantly enhanced by progressive fluorine substitution, the substitution of a hydrogen atom by a methyl group in the CH(3)X...NH(3) complex weakened the halogen bonding. Moreover, remote substituent effects have also been noted in the complexes of halobenzenes with different para substituents. The influence of the hybridization state of the carbon atom bonded to the halogen atom has also been examined and the results reveal that halogen-bond strengths decrease in the order HC triple bond CX > H(2)C=CHX approximately O=CHX approximately C(6)H(5)X > CH(3)X. In addition, several excellent linear correlations have been established between the interaction energies and both the amount of charge transfer and the electrostatic potentials corresponding to an electron density of 0.002 au along the R-X axis; these correlations provide good models with which to evaluate the electron-accepting abilities of the covalently bonded halogen atoms. Finally, some positively charged halogen-bonded systems have been investigated and the effect of the charge has been discussed. 相似文献
54.
55.
The self‐complementary tetrameric propargyl triols 8, 14, 18 , and 21 were synthesized to investigate the duplex formation of self‐complementary, ethynylene‐linked UUAA, AAUU, UAUA, and AUAU analogues with integrated bases and backbone (ONIBs). The linear synthesis is based on repetitive Sonogashira couplings and C‐desilylations (34–72% yield), starting from the monomeric propargyl alcohols 9 and 15 and the iodinated nucleosides 3, 7, 11 , and 13 . Strongly persistent intramolecular H‐bonds from the propargylic OH groups to N(3) of the adenosine units prevent the gg‐type orientation of the ethynyl groups at C(5′). As such, an orientation is required for the formation of cyclic duplexes, this H‐bond prevents the formation of duplexes connected by all four base pairs. However, the central units of the UAUA and AAUU analogues 18 and 14 associate in CDCl3/(D6)DMSO 10 : 1 to form a cyclic duplex characterized by reverse Hoogsteen base pairing. The UUAA tetramer 8 forms a cyclic UU homoduplex, while the AUAU tetramer 21 forms only linear associates. Duplex formation of the O‐silylated UUAA and AAUU tetramers is no longer prevented. The self‐complementary UUAA tetramer 22 forms Watson–Crick‐ and Hoogsteen‐type base‐paired cyclic duplexes more readily than the sequence‐isomeric AAUU tetramer 23 , further illustrating the sequence selectivity of duplex formation. 相似文献
56.
D. N. Dybtsev M. P. Yutkin E. V. Peresypkina A. V. Virovets Y. Hasegawa H. Nishihara V. P. Fedin 《Russian Chemical Bulletin》2007,56(9):1782-1786
The reaction of Co(NO3)2·6H2O with 1,3,5-benzenetricarboxylic acid (H3btc, trimesic acid) in DMF at 100 °C afforded the coordination polymer [Co3(dmf)6(btc)(Hbtc)(H2btc)]··9H2O (1) (dmf is N,N′-dimethylformamide, DMF). According to the X-ray diffraction study, the metal-organic coordination polymer is composed of
planar honeycomb (6,3) networks, in which the organic benzenetricarboxylate anions and the inorganic Co2+ cations play a role of three-connected nodes. Disordered water molecules are intercalated between the layers. A study of
the magnetic properties showed the presence of a weak antiferromagnetic coupling between the Co2+ ions (S = 3/2).
Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1719–1723, September, 2007. 相似文献
57.
58.
0IntroductionConstructionoflow鄄dimensionalorganic鄄inorgan鄄icsupramoleculararrayswithnovelpropertiesrepre鄄sentsnewdirectionsinsolid鄄statechemistry[1,2].Gener鄄allythephysicalpropertiesofsuchlowdimensionalcompoundsdifferfromthoseoftheparentcompound.Our 相似文献
59.
Paul V. Bernhardt Dr. Geoffrey A. Lawrance Brian W. Skelton Allan H. White 《无机化学与普通化学杂志》2007,633(7):1036-1039
Cations derived by protonation of the ligand title compound (L1) have been structurally characterized in their di‐ and tetra‐ protonated forms in the salts [H2L1][ClO4]2·2H2O and [H4L1][ZnCl4]2·4H2O. In both structures, one half of the formula unit comprises the asymmetric unit of the structure, the macrocycle being centrosymmetric, with the two macrocycles adopting similar conformations. In both salts, a pair of diagonally opposed macrocyclic secondary amine groups are protonated; in the [H4L1]4+ salt, the additional pair of protons are accommodated on the exocyclic pendant amine groups. The dispositions of the pendent amines differ between the two structures, being ‘equatorial’ with respect to the macrocyclic ring in the [H2L1]2+ salt, and ‘axial’ in the [H4L1]4+ salt. In other structurally characterized compounds containing [H4L1]4+ the equatorial disposition was found in the ferricyanide adduct, while in the tetraperchlorate salt the axial disposition was identified. The differences in disposition of the exocyclic groups are ascribed to the extensive H‐bonding in the lattices. 相似文献
60.
A new nickel(Ⅱ)-dicyanamide compound, [Ni(dca)2(en)]n (1) (dca=dicyanamide anion, [N(CN)2]-); en=ethylene diamine), has been synthesized and its structure has been determined by single crystal X-ray diffraction analysis. The crystal is monoclinic, space group P21/n with unit cell dimensions: a=0.694 3(1) nm, b=1.041 5(2) nm, c=1.4132(2) nm, and β=90.381°, Z=4, V=1.011 0(3) nm3. In this compound, the adjacent nickel atoms are connected by dca all in μ1,5-bridging mode to form ladder-like units, which are linked with double dca bridges to generate a regular infinite stair-like structure. Temperature-dependent magnetic susceptibility was also characterized for this compound. CCDC: 208276. 相似文献