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71.
A considerable improvement is reported in the iron-catalyzed ring-expansion reactions of epoxides generating tetrahydrofuran derivatives by formal insertion of an alkene. Optimization of the catalyst system revealed that a preformed [Fe(salen)] complex minimizes the formation of polymerization side-products so that increased yields of intermolecular reactions were obtained. However, more importantly, the scope of the reaction could also be enlarged considerably. The iron-catalyzed ring-expansion reaction can now be applied to some styrene oxide derivatives, acting as radical donors, as well as to a wide variety of acceptor-substituted acyclic alkenes and cyclic dienes that act as radical acceptors. The use of unsymmetrical radical acceptors led to interesting questions concerning the regiochemistry of the reactions. The conservation of the stereochemistry of the starting materials in the products was investigated through a study of the reactions of E- and Z-configured acceptor-substituted double bonds. The reactions of fumaric and maleic esters were performed and the ratios of diastereomeric and regioisomeric products were determined. 相似文献
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At weak force range the two-well Duffing equation has a closed bifurcation region in theparameter plane, inside which there are many different periodic windows. By means ofone-dimensional and two-dimensional symbolic dynamics, these periodic windows and thedynamical behavior of chaotic attractors are analyzed systematically. 相似文献
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Crystal Structure of the Isothiocyanato Complex [Ph3PNH2(OEt2)][Sm(NCS)4(DME)2] Colourless single crystals of [Ph3PNH2(OEt2)][Sm(NCS)4(DME)2] ( 1 ) have been obtained besides of Ph3PS from the reaction of the homoleptic phosphorane iminato complex [Sm(NPPh3)3]2 with carbon disulfide in THF solution, followed by recrystallisation from DME/Et2O. According to the crystal structure analysis 1 consists of [Ph3PNH2]+ cations with the diethylether molecule forming a N–H…O hydrogen bridge, and anions [Sm(NCS)4(DME)2]–. Sm3+ realizes coordination number eight by four nitrogen atoms of the isothiocyanato ions and by four oxygen atoms of the DME chelates. 1 : Space group P 1, Z = 4, lattice dimensions at 193 K: a = 919.0(1), b = 1965.2(2), c = 2401.3(2) pm, α = 96.748(11)°, β = 94.827(10)°, γ = 91.720(11)°, R = 0.029. 相似文献
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S. Anfang K. Harms F. Weller O. Borgmeier H. Lueken H. Schilder K. Dehnicke 《无机化学与普通化学杂志》1998,624(1):159-166
Phosphoraneiminato Complexes of Rare Earths Elements. Syntheses and Crystal Structures of [M2(C5H5)3(NPPh3)3] · 3 C7H8 mit M = Y, Dy, and Er. Magnetic Properties of [Dy2(C5H5)3(NPPh3)3] · 3 C7H8 The title compounds have been prepared by reactions of the cyclopentadienidchlorides [M(C5H5)2Cl]2 with LiNPPh3 in boiling toluene, and they were characterized by crystal structure determinations. All three compounds crystallize isotypicly with one another within the orthorhombic space group Pbca with Z = 8. Two of the three phosphoraneiminato groups link the metal atoms via μ2-N atoms to almost planar M2N2 four-membered rings. The third NPPh3– group is terminally bonded. The magnetic susceptibility of [Dy2(C5H5)3(NPPh3)3] · 3 C7H8 has been determined (SQUID magnetometer) in the temperature range 1.7 K–300 K at magnetic fields between 0.01 T and 5 T. Calculations based on a cubic ligand field model lead to a satisfactory simulation with reasonable ligand field parameters. The inclusion of isotropic intramolecular exchange interactions in the model does not improve the fit, so that in the framework of the applied model no hints to a spin-spin coupling within the dinuclear units are obtained. 相似文献
79.
Amido Ligands for the Synthesis of Polynuclear Lanthanoid Complexes By 1 : 1 reaction of LnBr3 with NaNHPh in THF the Rare-Earth Complexes [Ln2Br4(μ2-NHPh)2(thf)5] (Ln = Sm ( 1 ), Ln = Gd ( 2 )) with two bridging anilido ligands are obtained. In the system LnBr3/NaNHPh/(Me2SiO)3 the tetranuclear compounds [Ln4(μ4-O)(NHPh)3(OSiMe2NPh)6Na5(thf)7] · THF (Ln = Gd ( 3 ), Ln = Yb ( 4 )) can be built up. They have a central μ4-oxygene atom in the Ln4-tetrahedron. It has an oxa-dimethylsilyl-N-phenylamido ligand over all edges and an anilido ligand on three vertexes. By this reaction small amount of [Na4(thf)6Yb2(OSiMe2NPhSiMe2O)2(OSiMe2NPh)2(NHPh)2] ( 5 ) with a O- and N-bridged Yb–Na polyhedron and N-phenyl-bis(dimethylsilanolato)-ligands coordinating μ2-η2 with its oxygen atoms are obtained. Reaction of Lanthanideshalides with LiNHtBu leads to dimeric complexes. The formation of bridging oxasilylamido ligands is also observed. The compound [Li2Ln(OSiMe2NtBu)2(HNtBu)(thf)]2 (Ln=Sm ( 6 ), Gd ( 7 ) and Yb ( 8 )) contains now an O- and N-bridged Ln–Li polyhedron. (Crystal Data of 1–8 see ‘‘Inhaltsverzeichnis”︁”︁). 相似文献
80.
低地球轨道上的航天器易受到微流星体及空间碎片的超高速撞击,导致其严重的损伤甚至灾难性的失效。撞击损伤特性研究是航天器防护设计的一个重要问题。通过铝球弹丸超高速正撞击薄铝板的实验研究和数值模拟,证明了AUTODYN-2D软件数值模拟预测薄铝板超高速撞击穿孔直径的有效性。通过对弹丸直径、弹丸撞击速度和薄铝板厚度影响薄铝板超高速撞击穿孔直径的数值模拟,以及利用实验结果和数值模拟结果拟合的曲线,得到了铝球弹丸超高速撞击薄铝板的穿孔规律以及影响薄铝板超高速撞击穿孔直径的主要因素。 相似文献