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991.
Foltz C Stecker B Marconi G Bellemin-Laponnaz S Wadepohl H Gade LH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(35):9912-9923
The underlying conceptual differences in exploiting two- and threefold rotational symmetry in the design of chiral ligands for asymmetric catalysis have been addressed in a comparative study of the catalytic performance of bisoxazoline (BOX) and tris(oxazolinyl)ethanes (trisox) containing copper(II) Lewis acid catalysts. The differences become apparent in constructing new catalysts by systematically "deforming" the stereodirecting ligand by inverting chiral centres or replacing chiral by achiral oxazolines. The catalytic alpha-amination of ethyl 2-methylacetoacetate with dibenzyl azodicaboxylate, which occurs with high enantioselectivity for both Ph(2)-BOX and Ph(3)-trisox copper catalysts, has been employed as the test reaction. In the trisox-copper complex [Cu(II)(iPr(3)-trisox)(kappa(2)-O,O'-MeCOCHCOOEt)](+)[BF(4)](-) (1), which was characterised by X-ray diffraction, two of the oxazoline groups are coordinated to the central copper atom, whilst the third oxazoline unit is dangling with the N-donor pointing away from the metal centre. A similar arrangement is found for the stereochemically "mixed" C(1)-trisox complex [Cu(II){(Ph(3)-trisox(R,S,S)}(kappa(2)-O,O'-MeCOCHCOOEt)(H(2)O)](+)[ClO(4)](-) (2), in which the phenyl substituents adopt a first coordination sphere meso arrangement. The almost identical selectivity of the Ph(3)-trisox(R,R,R)- and Ph(2)-BOX(R,R)-derived catalysts is as expected from the proposed model of the active catalyst based on a partially decoordinated podand. The behaviour of the "desymmetrised" trisox-Cu catalysts may be rationalised in terms of a general steady-state kinetic model for the three possible active bisoxazoline-copper species, which are expected to be in rapid exchange with each other in solution. This applies to both the trisox derivatives with stereochemically inverted and achiral oxazoline rings. The study underscores previous observations of superior performance of the catalysts bearing C(3)-chiral stereodirecting ligands as compared to systems of lower symmetry. 相似文献
992.
以类层柱CuZnAl水滑石为前体,经不同温度焙烧制备了一系列甲醇水蒸气重整制氢催化剂. 在250 ℃、 水/甲醇比1.3和重时空速2.5 h-1下的反应结果表明, 600 ℃焙烧的催化剂具有优异的活性和稳定性,而≤500 ℃和≥700 ℃焙烧后的催化剂活性较差. 热重、 X射线衍射、 傅里叶变换红外光谱和程序升温还原分析结果表明, 600 ℃焙烧时水滑石分解较为完全,析出纳米CuO粒子的同时伴生CuAl2O4尖晶石相,进而在反应过程中对金属Cu纳米粒子和ZnO起到良好的隔离和稳定作用. 焙烧温度≥700 ℃时CuO纳米粒子发生二次团聚,同时CuAl2O4尖晶石相大量生成,造成催化活性位减少,活性较低; 而焙烧温度≤500 ℃时水滑石分解不完全,生成 (Cu,Zn)AlxOy(CO3)z复合物且无尖晶石相伴生,造成反应中金属Cu纳米粒子和ZnO聚集,导致催化剂活性较低. 相似文献
993.
994.
Hirotoshi Sakamoto Ryotaro Matsuda Dr. Sareeya Bureekaew Daisuke Tanaka Dr. Susumu Kitagawa Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(20):4985-4989
Broken switch : Guest‐accessible metal sites are generated on the pore surface of a porous coordination polymer (see figure) through the complementary coordination‐bond rearrangement in a single‐crystal‐to‐single‐crystal fashion, which is triggered by the removal of coordinated water.
995.
Mesu JG Visser T Beale AM Soulimani F Weckhuysen BM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(27):7167-7177
Structural analysis has been carried out on copper(II )–histidine (Cu2+/His) complexes after immobilization in the pore system of the zeolites NaY and de‐aluminated NaY (DAY). The aim of this study was to determine the geometrical structure of Cu2+/His complexes after encaging, to obtain insight into both the effect of the zeolite matrix on the molecular structure and redox properties of the immobilized complexes. In addition to N2 physisorption and X‐ray fluorescence (XRF) analyses, a combination of UV/Vis/NIR, ESR, X‐ray absorption (EXAFS and XANES), IR, and Raman spectroscopy was used to obtain complementary information on both the first coordination shell of the copper ion and the orientation of the coordinating His ligands. It was demonstrated that two complexes ( A and B ) are formed, of which the absolute and relative abundance depends on the Cu2+/His concentration in the ion‐exchange solution and on the Si/Al ratio of the zeolite material. In complex A , one His ligand coordinates in a tridentate facial‐like manner through Nam, Nim, and Oc, a fourth position being occupied by an oxygen atom from a zeolite Brønsted site. In complex B , two His ligands coordinate as bidentate ligands; one histamine‐like (Nam, Nim) and the other one glycine‐like (Nam, Oc). In particular the geometrical structure of complex A differs from the preferred structure of Cu2+/His complexes in aqueous solutions; this fact implies that the zeolite host material actively participates in the coordination and orientation of the guest molecules. The tendency for complex A to undergo reduction in inert atmosphere to Cu1+ (as revealed by dynamic XANES studies) suggests activation of complex A by the interaction with the zeolite material. EXAFS analysis confirms the formation of a distorted four coordinate geometry of complex A , suggesting that the combination of zeolite and one His ligand force the Cu2+ complex into an activated, entactic state. 相似文献
996.
A large specific surface area perovskite-type mixed oxide PbTiO3 supported cupric oxide was synthesized as a catalyst for NO decomposition and characterized by techniques such as XPS, XRD, H2-TPR before and after NO decomposition reactions. The catalytic properties were tested with a fix-bed micro-reactor. The results showed that the PbTiO3 was inactive for the reactions, but 1wt % Cu/PbTiO3 catalyst gave fairly good activities for NO decomposition at temperature as low as 473 K. Copper species were found well-dispersed but weakly interacted with the support before NO decomposition, and the NO decomposition caused significant change in the environment of the copper species, which became Cu(Ⅰ) and most probably incorporated into surface crystal lattice of the nano-sized PbTiO3. In NO reaction, a large amount of oxygen atoms from the decomposition of NO penetrated into the nano-sized PbTiO3 support and caused small expansion of crystal lattice. The transport of oxygen between the copper species and the catalyst support may be helpful to speed up the kinetic regeneration of active metal sites from oxygen occupancy and resulted in good catalytic performance. 相似文献
997.
水相中金属铜表面生成亚铜—邻菲罗啉配合物的反应 总被引:1,自引:0,他引:1
本文研究了零价铜在邻菲罗啉水溶液中的反应。当溶液敞露于空气并存在有机阴离子X-时,例如苯甲酸盐(Bz)、对甲基苯磺酸盐(Ts)等,铜的表面生成了致密的反应产物的薄层,经IR、UV/VIS、MS和元素分析证明了该薄层为相当纯的亚铜的邻菲罗啉配位化合物,结构为[Cu(phen)2]+X-。在乙醇/甲苯混合溶剂中得到了表面反应产物的晶体[Cu(phen)2](CH3C4H6SO3)C2H5OH,并用X-ray测得了结构。本工作表明溶液中的CuⅡ离子抑制Cu0氧化成CuⅠ而影响反应层的形成,同时又促进CuⅠ氧化成CuⅡ的过程 相似文献
998.
The synthesis, structure, and spectroscopic characterization of a series of phenylacetylenylene rodlike molecules containing dipyrromethene (dipyrrin) ligands are described. The combination of the phenylacetylenylene groups with the porphyrinogenic dipyrrin moieties results in a rich absorption spectroscopy for these compounds, although the fluorescence of the phenylacetylenylene moiety is quenched by presence of the dipyrrin chelator. The Cu(2+) and Fe(3+) complexes of these ligands have been prepared and three of these compounds have been structurally characterized by using single-crystal X-ray diffraction. Unlike other octahedral metal-dipyrrin complexes described to date, one of the iron complexes demonstrates ideal threefold symmetry in the solid-state. The elongated structure and high symmetry of these complexes suggests the use of these meso-substituted phenylacetylenylene ligands as an interesting class of extended, branched molecules for the construction of supramolecular architectures. 相似文献
999.
A selective Spectrophotometric method has been developed for the trace determination of copper after adsorption of its 1-phenyl-4,4,6-trimethyl(1H, 4H)-pyrimidine-2-thiol (PTPT) complex onto microcrystalline naphthalene. The complex is quantitatively adsorbed on naphthalene in the pH range 7.5–11.5, separated by filtration, dissolved in dimethylformamide (DMF) and determined spectrophotometrically at 400 nm. Beer's law is obeyed in the concentration range 2.5–37.5 g of copper in 10 ml of DMF. The molar absorptivity and Sandell's sensitivity are 1.30 × 1041 · mol–1 · cm–1 and 0.0048g cm–2, respectively. Ten replicate analyses of a solution containing 20.0 g of copper gave a mean absorbance of 0.410 with a relative standard deviation of 0.91 %. The interferences of various ions have been studied and the method has been validated by the determination of copper in various standard reference materials, beers, wines, human hair, goat liver and environmental samples.On leave from St. Stephen's College, Delhi 110 007, India 相似文献
1000.
3类手性配体d-10-樟脑磺酸及其衍生物,α-(-)-羟蒎酮及其衍生物,又恶唑啉6衍生物分别与铜(Ⅱ)形成手性铜配合物,催化重氮乙酸酯与1,1-二苯乙烯或异丁烯的环丙烷化加成反应,得到光学活性环丙羧酸酯,不对称诱导最高可达95%e.e.。 相似文献