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991.
Kristian Lappalainen Katariina Yliheikkil Adnan S. Abu‐Surrah Mika Polamo Markku Leskel Timo Repo 《无机化学与普通化学杂志》2005,631(4):763-768
Iron(II) and cobalt(II) complexes ( 7 ‐ 15 ) based on new aldimine 2, 6‐bis[(imino)methyl]pyridine ( 1 , 2 , 4 , 6 ) and ketimine (2, 6‐bis[(imino)ethyl]pyridine ( 3 , 5 ) ligands with bulky chiral aliphatic or aromatic terminal groups have been prepared and characterized by 1H NMR, 13C NMR, IR‐, mass spectroscopy (EI), and elemental analysis. The complex [CoCl2(BBoMP)]·1/2 CHCl3 ( 13 ) (BBoMP: 2, 6‐bis{(R‐(+)‐(bornylimino)‐methyl}pyridine) crystallizes in monoclinic space group P21 with cell dimensions: a = 7.6603(11) Å, b = 28.3153(14) Å, c = 13.537(2) Å, V = 2908.1(6) Å3, Z = 4. The coordination sphere around Co is distorted trigonal bipyramidal. 相似文献
992.
The molar heat capacity of the azeotropic mixture composed of ethanol and toluene was measured by a high precision adiabatic calorimeter from 80 to 320 K. The glass transition and phase transitions of the azeotropic mixture were determined based on the heat capacity measurements. A glass transition at 103.350 K was found. A solid-solid phase transition at 127.282 K, two solid-liquid phase transitions at 153.612 and 160.584 K were observed, which correspond to the transition of metastable crystal to stable crystal of ethanol and the melting of ethanol and toluene, respectively. The thermodynamic functions and the excess ones of the mixture relative to the standard temperature 298.15 K were derived based on the relationships of the thermodynamic functions and the function of the measured heat capacity with respect to temperature. 相似文献
993.
Triazene‐substituted arylboronic esters were prepared readily from the corresponding aryl magnesium derivatives and shown to function as a new class of donor–acceptor‐substituted coupling reagents. The selective functionalization of these aromatic derivatives led to a wide variety of terphenyl derivatives in which the original bifunctional unit (often further substituted with another functional group) formed the central aromatic ring. The functionalized terphenyl derivatives were formed in two efficient cross‐coupling steps from the triazene‐substituted boronic esters: Suzuki cross‐coupling with an aryl halide was followed by BF3?OEt2‐induced palladium‐catalyzed coupling of the diazonium salt generated in situ from the triazene with an arylboronic acid. 相似文献
994.
Heekyoung Choi Sojeong Heo Seonae Lee Ka Young Kim Jong Hyeon Lim Sung Ho Jung Shim Sung Lee Hiroyuki Miyake Jin Yong Lee Jong Hwa Jung 《Chemical science》2020,11(3):721
We report kinetically controlled chiral supramolecular polymerization based on ligand–metal complex with a 3 : 2 (L : Ag+) stoichiometry accompanying a helical inversion in water. A new family of bipyridine-based ligands (d-L1, l-L1, d-L2, and d-L3) possessing hydrazine and d- or l-alanine moieties at the alkyl chain groups has been designed and synthesized. Interestingly, upon addition of AgNO3 (0.5–1.3 equiv.) to the d-L1 solution, it generated the aggregate I composed of the d-L1AgNO3 complex (d-L1 : Ag+ = 1 : 1) as the kinetic product with a spherical structure. Then, aggregate I (nanoparticle) was transformed into the aggregate II (supramolecular polymer) based on the (d-L1)3Ag2(NO3)2 complex as the thermodynamic product with a fiber structure, which led to the helical inversion from the left-handed (M-type) to the right-handed (P-type) helicity accompanying CD amplification. In contrast, the spherical aggregate I (nanoparticle) composed of the d-L1AgNO3 complex with the left-handed (M-type) helicity formed in the presence of 2.0 equiv. of AgNO3 and was not additionally changed, which indicated that it was the thermodynamic product. The chiral supramolecular polymer based on (d-L1)3Ag2(NO3)2 was produced via a nucleation–elongation mechanism with a cooperative pathway. In thermodynamic study, the standard ΔG° and ΔHe values for the aggregates I and II were calculated using the van''t Hoff plot. The enhanced ΔG° value of the aggregate II compared to that of the formation of aggregate I confirms that aggregate II was thermodynamically more stable. In the kinetic study, the influence of concentration of AgNO3 confirmed the initial formation of the aggregate I (nanoparticle), which then evolved to the aggregate II (supramolecular polymer). Thus, the concentration of the (d-L1)3Ag2(NO3)2 complex in the initial state plays a critical role in generating aggregate II (supramolecular polymer). In particular, NO3− acts as a critical linker and accelerator in the transformation from the aggregate I to the aggregate II. This is the first example of a system for a kinetically controlled chiral supramolecular polymer that is formed via multiple steps with coordination structural change.The nanoparticles were transformed into the supramolecular polymer as the thermodynamic product, involving a helical inversion from left-handed to right-handed helicity. 相似文献
995.
Voltammetry of immobilized microparticles was used to study the electrochemistry of the raw pigments that produce the metallic lustre on ceramics after a successful firing. To study this influence of the mixture components on the reduction properties to achieve the metallic lustre, 14 mixtures of illitic clay, Fe2O3, HgS, CuO and AgNO3 were prepared and studied in different media. Iron oxide improves the yield of the reduction of the metals and cinnabar helps a closer reduction of silver to copper reduction and prevents the Ag? Cu alloying because of the formation of silver–mercury adducts. The presence of one of the metals influences the peak position of the other metal. The use of vinegar as diluting agent is not casual, because in this media the reduction of silver takes place at a potential closer to the copper. This electroanalytical technique allowed to distinguish between powders of different composition and offered some information about the role of the components in the reduction of copper and silver and the selection of vinegar to prepare the raw pigment suspensions. 相似文献
996.
Jian‐Hua Zhao Hsuan‐Liang Liu Hsin‐Yi Lin Chih‐Hung Huang Hsu‐Wei Fang Shau‐Wei Tsai 《中国化学会会志》2007,54(4):835-842
In this study, we present the results from the semiempirical molecular orbital calculations for the acylation step in the lipase‐catalyzed ester hydrolysis. The results reveal that the lowest energy path for the formation of the tetrahedral intermediate is for the serine residue of the catalytic triad to attack the substrate, followed by coupling heavy atom movement and proton transfer. The calculations of four active site models show that the cooperation of the aspartate group and the oxyanion hole is capable of lowering the activation energy by about 16 kcalmol?1. Our results further suggest that the lipase‐catalyzed ester hydrolysis adopts the single proton transfer mechanism. 相似文献
997.
Weakly bound linear and bent dimers, FH—X (where X = CO, OC, CNH, NCH, N2O and ON2), are investigated using the DFT B3LYP and ab initio MP2 methods with the same basis sets (6–311++G(3df,2pd)). The strengths of the H—C or H—N H‐bonds in dimers FH—CO, FH—CNH, and FH—N2O are compared with those of the H—O or H—N H‐bonds in dimers FH—OC, FH—NCH, and FH—ON2. The results obtained for the H‐bond distances, the elongation effect of the HF bond, the red shift of the HF stretching frequency, and the energy difference between the dimer and the charge transfer reveal that the H‐bonds of the first group of dimers are stronger than those of the second. The Gibbs energies calculated for the six dimer formations indicate that the weakly bound dimers are unstable at room temperature (T = 298 K) (FH—X's → FH + X's, ΔG < 0). 相似文献
998.
Three novel Schiff base cadmium(II) complexes, derived from the end‐on (μ‐1,1‐N3) azide or end‐to‐end (μ‐1,3‐NCS) thio cyanate bridges and similar tridentate Schiff base ligands, have been synthesized under similar synthetic procedures and their crystal structures determined by X‐ray diffraction methods. They are the dinuclear double end‐on azide‐bridged [Cd2(L1)2(N3)2(μ‐1,1‐N3)2] ( 1 ), the dinuclear double end‐on azide‐bridged [Cd2(L2)2(N3)2(μ‐1,1‐N3)2] ( 2 ), and the dinuclear double end‐to‐end thiocyanate‐bridged [Cd2(L3)2(NCS)2(μ1,3‐NCS)2] ( 3 ), where L1, L2 and L3 are three similar tridentate Schiff bases obtained by condensation of 2‐pyridylaldehyde with N,N‐diethylethane‐1,2‐diamine, of 2‐pyridylaldehyde with N‐isopropylethane‐1,2‐diamine, and of 2‐pyridylaldehyde with N,N‐dimethylpropane‐1,3‐diamine, respectively. Each cadmium(II) centre in the complexes is in a distorted octahedral coordination. There is a crystallographic inversion centre in each of the complexes. The similar small ligands used as the secondary ligands in the preparation of the cadmium(II) complexes with similar Schiff bases can result in similar structures. 相似文献
999.
Metabolic fingerprinting of Ephedra species using 1H-NMR spectroscopy and principal component analysis 总被引:4,自引:0,他引:4
Kim HK Choi YH Erkelens C Lefeber AW Verpoorte R 《Chemical & pharmaceutical bulletin》2005,53(1):105-109
The metabolomic analysis of Ephedra species was performed using 1H-NMR spectroscopy and multivariate data analysis. A broad range of metabolites could be detected by 1H-NMR spectroscopy without any chromatographic separation. The principal component analysis used to reduce the huge data set obtained from the 1H-NMR spectra of the plant extracts clearly discriminated three different Ephedra species. The major differences in Ephedra sinica, Ephedra intermedia and Ephedra distachya var. distachya were found to be due to benzoic acid analogues in the aqueous fraction and ephedrine-type alkaloids in the organic fraction. Based on this metabolomic recognition, one of nine commercial Ephedra materials evaluated was shown to be a mixture of Ephedra species. This method will be a useful tool for chemotaxonomic analysis and authentification of Ephedra species including quality control of plant materials. 相似文献
1000.
Aliphatic and aromatic 1,3‐dithiane are oxidized to the corresponding carbonyl compounds in good yields under mild conditions by N,N′‐diiodo‐N,N′‐1,2‐ethanediyl‐bis(p‐toluenesulphonamide) [NIBTS] and silver nitrate. 相似文献