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21.
手性胺醇稀土配合物的合成、荧光性质及其催化芳香酮的不对称氢化反应 总被引:2,自引:0,他引:2
合成了三种新的含C2-对称轴的手性胺醇(PhOHCHCH2)2NCH2C6H4R (R=OCH3, L1; R=CH3, L2; R=Cl, L3), 将其与无水氯化稀土LnCl3•4THF (Ln=La, Sm, Gd)反应生成了九个新的胺醇类稀土配合物LLnCl•2THF (L=L1, L2, L3; Ln=La, Sm, Gd). 用元素分析、热重分析、红外和紫外光谱等手段对它们进行了表征. 荧光光谱显示一些配合物具有荧光性能. 原位催化芳香酮的不对称氢化反应表明: L1/SmCl3•4THF体系催化苯乙酮不对称氢化反应的转化率达71%, 相应的对映体过量值达32%. 相似文献
22.
U. M. Dzhemilev F. A. Selimov R. A. Khusnutdinov A. A. Fatykhov E. I. Andreikov G. A. Obanin 《Russian Chemical Bulletin》1992,41(5):895-902
Liquid-phase condensation of 3-, 4-, and 8-aminoquinolines with aliphatic and aromatic aldehydes catalyzed by transition and rare-earth metal complexes is an efficient method for synthesis of substituted 1,7- and 1,6-naphthyridines and 1,10-phenanthrolines.Institute of Organic Chemistry, Ural Branch, Russian Academy of Sciences, 450054 Ufa; Eastern Scientific-Research Institute of Coal Chemistry, 620219 Sverdlovsk. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1139–1148, May, 1992. 相似文献
23.
合成了一种新的芳香族酰胺配体2,2’-(1,2-亚苯基二氧)二(N-苯基乙酰胺)及其稀土(La,Eu,Tb,Dy,Sm,Gd)硝酸盐配合物,通过核磁共振谱、元素分析、摩尔电导、红外光谱、差热等测试技术对其进行了结构表征。结果表明,稀土配合物的可能结构为:[REL(NO3)3]·H2O(RE:La^3+、Sm^3+、Eu^3+、Gd^3+、Tb^3+、Dy^3+).配合物产率约为78%。在稀土配合物中,作为抗衡阴离子的3个硝酸根均以双齿的配位方式与稀土配位,稀土配位数为10,并且还有1个结晶水。在298K下对配合物[EuL(NO3)3]·H2O和[TI)L(N03)3]·H2O的固体荧光性质进行了研究。结果发现,它们分别发射Eu^3+和Tb^3+稀土离子的特征荧光,且配合物[TbL(NO3)3]·H2O的荧光比[EuL(NO3)3]·H2O的荧光强。说明此芳香族酰胺配体敏论Tb^3+发光比敏化Eu^3+发光程度大。 相似文献
24.
Hiléia K. S. Souza V. R. da Silveira F. M. M. Borges Dulce M. A. Melo H. Scatena Jr. O. A. de Oliveira A. G. Souza 《Journal of Thermal Analysis and Calorimetry》2007,87(2):433-436
Thermal behavior of rare earth nitrate complexes
with 2-azacyclononanone (AZA) with Ln(NO3)3·3(AZA)
composition (where Ln=Gd, Er and Ho) was
analyzed in kinetic point of view. Kinetic parameters were calculated from
thermogravimetric data. All obtained results were similar. The first decomposition
step was representative to the loss of ligand and the residue was essentially
Ln2O3. Furthermore, a reaction
path was proposed for the thermal decomposition of the Ln(NO3)3·3(AZA). 相似文献
25.
M. Iwan R. Łyszczek A. Ostasz Z. Rzączyńska 《Journal of Thermal Analysis and Calorimetry》2007,88(1):157-162
Properties of lanthanide 1,2,4-benzenetricarboxylates and lanthanide
1,2,4,5-benzenetetracarboxylates obtained by a classical synthesis method
and under hydrothermal conditions were compared. Solid 1,2,4-benzenetricarboxylates
and 1,2,4,5-benzenetetracarboxylates of cerium, neodymium and erbium were
prepared by a classical precipitation method. The same lanthanide compounds
were obtained also from hydrothermal reaction. All obtained products were
examined by elemental analysis. General formulae of complexes were: Ln(1,2,4-btc)·xH2O and Ln4(1,2,4,5-btec)3·yH2O. The thermal analysis
shows that hydrothermal conditions cause the coordination of less number of
water molecules to complex molecule. Because lanthanide ions exhibit the most
often the coordination number equal 8 or 9 one can conclude that the coordination
ability of carboxylic groups under hydrothermal conditions is different from
that under mild ones. Probably, in hydrothermal conditions the carboxylic
groups of 1,2,4-benzenetricarboxylate ions are able to form more coordination
bonds with lanthanide ions than under normal pressure. 相似文献
26.
Radiationless transitions in lanthanide ions embedded in glassy and crystalline hosts have been briefly reviewed. The correlations
of multiphonon relaxation rates with energy gaps, vibrational frequencies, temperatures and electronic symmetries have been
discussed. The essence of various theories, such as Nth order methods, non-adiabatic Hamiltonian method, dynamic coupling
model has also been presented. 相似文献
27.
Cheng Zhang Laurence Bensaid Donna McGregor Xikui Fang Robertha C. Howell Benjamin Burton-Pye Qunhui Luo Louis Todaro Lynn C. Francesconi 《Journal of Cluster Science》2006,17(2):389-425
Lanthanide complexes of polyoxometalates, including the α2-P2W17O61
10− ligand, have been pioneered by Michael T. Pope, to whom this paper is dedicated. Examination of the solid-state and solution behavior of lanthanide complexes of the α2-P2W17O61
10− ligand are reported here to identify trends that will facilitate rational synthesis of hybrid organic lanthanide polyoxometalate complexes. Therefore, combining our data with that obtained by Pope and others a number of trends come into view. It is clear that there are two structural types for the 1:1 or 2:2 [Ln(H2O)X(α2-P2W17O61)]2
14− species. The early lanthanides show a “cap to cap” structure that allows the Ln ion to be 9 coordinate and accommodates the longer bond lengths. The mid-late lanthanides show a “cap to belt” structure that allows the lanthanides to be 8 coordinate; this structural type is appropriate for the shorter bond lengths of the later lanthanides. The 1:1⇌1:2 equilibrium, that was observed by Pope for the Ce(III) analog is prevalent for the early- mid lanthanides. This equilibrium is slightly dependent on pH; however, cations have a major influence on this equilibrium. Larger, poorly hydrated cations appear to favor the 1:2 species for the early to mid lanthanides. Cations do not appear to influence the equilibrium for the later lanthanides; for all counterions, the 1:1 species was stable with no trace of the 1:2 species. Stability constants, K1 and K2, for the early to mid lanthanides were measured in this study by a competitive method and compared well with other published stability constant determinations. We suggest that the stability constants are not only dependent on the strength of interaction of the Ln with the α2-P2W17O61
10− ligand, but are also significantly influenced by the medium. The medium may bias the equilibria of the early-mid lanthanides and later lanthanides. The log K1/log K2 ratios are very close, suggesting that it is difficult to separate the 1:1 and 1:2 Ln: α2-P2W17O61
10− species.Electronic Supplementary Material Supplementary material for this article is available at and is accessible for authorized users.This paper is dedicated to Professor Michael T. Pope in honor of his substantial and sustained contributions to polyoxometalate chemistry and his inspiration to scientists working in the field. 相似文献
28.
Jerzy Lisowski Marta Paluch Tadeusz Lis 《Journal of inclusion phenomena and macrocyclic chemistry》2006,55(1-2):123-129
The template condensation of (R)-2,2′-diamino-1,1′-binaphthyl and 2,6-diformylpyridine leads to lanthanide(III) complexes of the new chiral hexaaza macrocycle L that adopts highly twisted conformation in [LnL](NO3)3 complexes. The complexes have been characterised by ESI MS spectrometry and NMR spectroscopy. The analogous N2O4 chiral crown ether L2 that has the same carbon skeleton as L does not exhibit tendency to bind lanthanide(III) ions. The X-ray crystal structure of L2 exhibit squeezed conformation of the macrocycle and spatial disposition of donor atoms that does not predispose it for coordination of lanthanide(III) ions. 相似文献
29.
30.
João Paulo R.F. André Hugh D. Burrows Carlos F.G.C. Geraldes Maria Da Graça M. Miguel M.Helena S.F. Teixeira L.F. Vilas Boas 《Polyhedron》1996,15(24):4331-4340
Complexation of europium(III) with glyceryl-1- and -2-phosphates has been studied by metal ion luminescence, 1H and 13C NMR spectroscopy and potentiometry. From the luminescence and NMR studies, the formation of a 1:1 inner-sphere complex, in which the glyceryl phosphate is directly bound to the metal, is confirmed. Similar apparent binding constants at pH 2 were obtained by the three methods. Values obtained by NMR at pH 2 are 53 M−1 and 12 M−1 for glyceryl-1- and -2-phosphate, respectively. By comparison with literature data on related systems it is suggested that the ligands bind through the phosphate group. To obtain structural information from the NMR data, complexation has also been studied with the lanthanide ions Dy(III), Er(III) and Gd(III) using both chemical shift and relaxation data. From this, metal-proton distance ratios have been calculated. Comparison of 1H and 13C NMR spectral data in the presence of paramagnetic lanthanides suggests conformational equilibria in the solutions. From the potentiometric studies, global formation constants have been determined, and speciation diagrams obtained over the pH range 1.5pH7.0 for ligand/metal ratios of 1 and 30. Implications of these results on lanthanide induced fusion of phospholipid membranes are discussed. 相似文献