二溴水杨醛异烟酰腙的合成及其与钪的荧光反应研究

合成了新荧光试剂３，５－二溴水杨醛异烟酰腙（简称ＤＢＳＩＮ），研究了该试剂与钪的荧光反应，在ｐＨ４．７～５．５乙醇／水溶液中，试剂与钪所形成的荧光络合物的λｅｘ＝３３５．４ ｎｍ、λｅｍ＝５１０ｎｍ．提出了混合稀土氧化物中微量钪的测定法。     

Influence of the composition of composites based on Y-and Sc-stabilized zirconium dioxide on catalytic properties in the oxidative conversion of methane

The effect of the composition of composites based on Y-and Sc-stabilized zirconium dioxide doped with CeO₂ and transition metal (Cu, Co, Ni) oxides on catalytic properties in the oxidative conversion of methane was studied. The activity of the composites correlated with the quantity and mobility of oxygen in them. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 3, pp. 184–188, May–June, 2006.     

Are Sc—C and Sc—P Bonds Reactive in Scandium Phosphinoalkylidene Complex? Insights on a Versatile Reactivity

The peculiar electronic structure of scandium phosphinoalkylidene complex [LSc{C(SiMe₃)PPh₂}THF] (L=[MeC(NDIPP)CHC(NDIPP)Me]⁻), DIPP=2,6‐(ⁱPr)₂C₆H₃) leads to an interesting versatile reactivity, which is demonstrated both experimentally and computationally. The complex undergoes [2+2] cycloaddition reactions with alkynes, and easily activates various X—O bonds such as C—O of propylene oxide, N—O of 3,5‐dimethylisoxazole, B—O of pinacolborane and Si—O of triethoxysilane. These reactions occur on the Sc—C bond of the phosphinoalkylidene complex. Interestingly, the Sc—P bond can also be activated as the presence of a Sc—C—P three center π interaction in the complex allows performing C—F activation of 2,6‐difluoropyridine and 1,2 addition with imine or ketone. The complex also reacts with metal complexes, [(COD)RhCl]₂ and (Ph₃P)AuCl, to form structural intriguing heterobimetallic complexes.     

Asymmetric Synthesis of Tetrahydroindolizines by Bimetallic Relay Catalyzed Cycloaddition of Pyridinium Ylides

A highly enantioselective synthesis of tetrahydroindolizines by catalytic multicomponent cycloaddition reactions of diazoacetate, pyridine, and alkenyloxindole was developed. Under the relay catalysis, involving an achiral iron(III) catalyst and chiral N,N′‐dioxide‐scandium(III) complex, a series of tetrahydroindolizines bearing different substituents were obtained in moderate to high yields (up to 99 %) with excellent diastereo‐ and enantioselectivities (up to >19:1 d.r., 99 % ee).     

邻菲罗啉单氮氧化物与钪(Ⅲ)钇(Ⅲ)配合物的合成与性质

邻菲罗啉单氮氧化物(PhenNO),分子内存在较大的共轭π键,对过渡金属离子具有良好的配位性能,其中某些配合物具有荧光。迄今为止,Sc、Y与该配体的配合物尚未见文献报道。本文在非水介质中合成出Sc(Ⅲ)、Y(Ⅲ)盐与PhenNO的五个新配合物,研究了它们的组成及其有关性质。由于Sc(Ⅲ)和Y(Ⅲ)的离子半径不同,它们的配位行为及其配合物的性质应有差异,试验结果证实了预测的结果。     

PMBP为载体的乳状液膜提取钪的研究

研究了以１－苯基－３－甲基－４－苯甲酰基吡唑酮－５（ＰＭＢＰ）为流动载体的乳状液膜（ＥＬＭ）法提取钪，确定最佳液膜体系组成为０．４％ＰＭＢＰ－３％Ｓｐａｎ８０－５％液体石蜡－煤油－３ｍｏｌ／ＬＨＣｌ，Ｒｏｉ＝１：１（油内比）．Ｒｗｅ（水乳比）可达２０：１．用该体系对钪与混合稀土进行分离，钪的回收率可达９５．５％，分离系数β（ＳＣ／ＲＥ）＝３２．０。     

Structure of ScBr3 and Sc2Br6 molecules determined by the synchronous gas-phase electron diffraction and mass spectrometric experiment and quantum chemical calculations

The structure of monomeric and dimeric molecules of scandium tribromide is studied by the synchronous electron diffraction and mass spectrometric experiment at T = 888(10) K and also by the quantum chemical calculations. The experimental data on the structural parameters of ScBr₃ molecule were obtained for the first time; also for the first time the molecular structure of Sc₂Br₆ dimeric molecule was studied. It is found that the ScBr₃ molecule has the C _3v effective configuration with the distance r _g (Sc-Br) = 2.430(3) Å and the valence angle ∠_g(Br-Sc-Br) = 117.6(5)°. The equilibrium structure of the given molecule is planar with D _3h symmetry. According to a theoretical study by DFT and MP2 methods, Sc₂Br₆ molecule has the equilibrium structure of D _2h symmetry with four Sc-Br bridge bonds. It was confirmed by the results of the electron diffraction analysis.     

高聚合度聚磷酸铵中特征磷的31P核磁共振分析

采用一维³¹P核磁共振(³¹P NMR)、 二维J分解谱(J-resolved)和扩散核磁(³¹P DOSY)等方法, 研究了高聚合度聚磷酸铵(APP)和多聚磷酸盐的特征磷及其偶合常数. 研究表明, 多聚磷酸盐及其中所含的二聚磷酸盐端基磷分别呈双峰和单峰特征, 多聚磷酸盐自旋偶合裂分的端基磷共振峰的偶合常数为19.4 Hz. APP中含有小分子二聚磷酸铵和正磷酸铵, 用³¹P NMR定量表征APP聚合度时需排除二聚体端基磷峰的面积. 在100 ℃水中溶解APP制备的APP水溶液中, 部分高聚合度APP发生断链, 中间磷共振峰处出现短链APP的磷共振峰.