Schiff碱双核Mn配合物的合成、结构和性能研究

Five manganese complexes of Schiff base were synthesized： [Mn^Ⅳ，Ⅳ(μ-O)(Salen)]₂·DMF·H₂O (1)， [Mn^Ⅳ，Ⅳ(μ-O)(5-BrSalen)]₂·DMF·0.5H₂O (2)， {Mn^Ⅳ，Ⅳ(μ-O)[Sal(1，2-pn)]}₂·H₂O (3)， {Mn^Ⅳ，Ⅳ(μ-O)[5-Br-Sal(1，2-pn)]}₂·H₂O (4)， {Mn^Ⅳ，Ⅳ(μ-O)[5-CH₃-Sal(1，2-pn)]}₂·2H₂O (5)， and were characterized by element analysis， IR and UV-Vis spectra. The results of cyclic voltammogram show that Schiff base ligands can drop the potential of manganese and steady high oxide state of manganese. The magnetic properties of 1 and 3 have also been studied. The results show that there is a weak ferromagnetically coupling of Mn^Ⅳ₂ pair at room and low temperature， and the interactions of complex 3 are weaker than complex 1.     

Synthesis of Sulfur-Containing Bis-Terpenoids Based on Monoterpene Oxides

Ethanedithiol and di(mercaptoethyl)sulfide react regio- and stereoselectively with (+)-3-carene and -hydroxy(-)--pinene -oxides in the presence of sodium ethoxide to give the corresponding bis- and tris-sulfides with two terpene fragments     

ZrxTixAl1-2xO2的制备及其在三效催化剂上的应用

Zr_0.5Ti_0.5O₂(ZT) and Zr_0.25Ti_0.25Al_0.5O₂(ZTA) mixed oxides were prepared by co-precipitation method and characterized by low temperature adsorption-desorption， XRD and NH₃-TPD. The activity of Pt/Zr_0.5Ti_0.5O₂ and Pt/ Zr_0.5Ti_0.5Al_0.5O₂ catalysts was evaluated using the simulated gases. The results show that ZTA samples exhibit higher specific surface area， larger pore volume and proper surface acidic amount and acidity in comparison with ZT. The results of the catalytic test indicate that Pt/ZT and Pt/ZTA catalysts exhibit excellent low-temperature catalytic activity and lower light-off temperatures of hydrocarbon， carbon monoxide and nitrogen oxides， especially better conversion for nitrogen oxides (NO_x). The addition of Al₂O₃ into ZT enhanced the anti-aging property of Pt/ ZTA catalysts due to the excellent textural， structural， surface acidity and thermal stability.     

Bioinspired manganese complexes catalyzed epoxidation for the synthesis of the epoxyketone fragment of carfilzomib

We report herein an efficient catalytic epoxidation reaction for the synthesis of epoxyketone (tert-butyl ((S)-4-methyl-1-((R)-2-methyloxiran-2-yl)-1-oxopentan-2-yl)carbamate), which is an important synthetic intermediate of carfilzomib.     

M_nP_m~+原子簇结构的ab initio从头算(M=Cr,Mn,n=1～3,m=2～12)

应用ahinitio计算程序，我们对飞行时间质谱产生的谱图进行了理论分析。稳定的MnnPm+和CrnPm+的结构基本上是多面体，仅有少数结构为环状和平面的。在计算中，我们尚未发现有链状的簇合物，这与风簇绝大多数是多面体是相一致的。因此，单枚金属簇合物的形成机制很大可能是金属进入磷形成的笼簇中。一般地说，除了磷的个别笼状团簇外，金属和磷相互成键是普遍存在的；在二核、多核金属磷簇合物中，金属间相互作用不常见，绝大多数是通过桥磷相连的。     

New organosols of nickel sulfides,palladium sulfides,manganese sulfide,and mixed metal sulfides and their use in preparation of semiconducting polymer-metal sulfide composites

Organosols of NiS, PdS, and MnS in N,N-dimethylformamide were prepared by reaction of the metal acetate with H₂S. Organosols of mixed-metal sulfides (Zn _x Cd_1–x S, Hg _x Cd_1–x S, Hg _x Cu_1–x S, Cd _x Mn_1–x S, Hg _x Mn_1–x S, Hg _x Cd_1–x S, and Mn _x Zn_1–x S) were similarly obtained by reaction of mixtures of the metal salts with H₂S. The organosol of Zn_0.5Cd_0.5S contained particle with two particle size distributions centered at 6.5 nm and 29 nm, as revealed by Ar laser-scattering analysis. The metal sulfides are recovered by addition of Et₂O to the organosols. Zn _x Cd_1–x S thus obtained shows magnetic susceptibility in the range 0.5×10^–6–2.3×10^–6 emug^–1 depending on thex value. Addition of polymers to the organosols affords semiconducting films of metal sulfide-polymer composites.     

Structural materials: metal-silicon-Boron. The Nb-rich corner of the Nb-Si-B system

Phase equilibria in the Nb-Nb₅Si₃-NbB region were studied in the melting (crystallization) range by means of light microscopy, XRD, SEM and EMPA on alloys after arc-melting and annealing at 1800°C and at subsolidus temperatures. Phase transition and melting temperatures were determined by DTA and pyrometric Pirani-Alterthum technique resulting in a solidus projection and two isopleths, Nb₇₇Si₂₃-Nb₇₇B₂₃ and Nb₉₉Si₁-Nb₅Si₂B. The T₂-phase Nb₅Si_3−xB_x (0?x?2, Cr₅B₃-type) was found to form equilibria with (Nb), NbB, Nb₃Si, and with the T₁-phase (Mn₅Si₃ derivative type). The T₂-phase melts incongruently (Nb₅Si_1.8B_1.2 at 2245°C) and forms a quasibinary eutectic with the niobium solid solution on a minimum tie-line at ∼1880°C.     

Rapid Synthesis of Nanocrystalline TiO2/SnO2 Binary Oxides and Their Photoinduced Decomposition of Methyl Orange

A rapid and simple method, the so-called stearic acid method (SAM) was developed to prepare nanostructured TiO₂/SnO₂ binary oxides by combustion of stearic acid precursors. The preparative process was studied by Fourier transform infrared spectroscopy (FT-IR). During the preparative process, metal precursors were dispersed in stearic acid at molecular level. Microstructure of the samples was investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), BET specific surface area measurement and the results were compared with those obtained by conventional sol-gel method. The photocatalytic decomposition of methyl orange was used as a model system to determine the relative influences of the preparation method and the concentration of SnO₂ on the photocatalytic activities. It was found that preparative methods affected the crystalline structure of TiO₂/SnO₂ powders and the anatase phase of TiO₂ was stabilized by the addition of SnO₂ in SAM. The samples prepared by SAM showed better dispersity, larger specific surface area and the TiO₂/SnO₂ (r=0.15, SAM) catalyst showed higher photocatalytic activity than Degussa P25.