Studies on Solid State Reactions of Coordination Compounds（LXXI）──Solid State Reactions of o－Aminobenzoic Acid with Copper（Ⅱ） Acetate and Formate at Room Temperature

ＳｔｕｄｉｅｓｏｎＳｏｌｉｄＳｔａｔｅＲｅａｃｔｉｏｎｓｏｆＣｏｏｒｄｉｎａｔｉｏｎＣｏｍｐｏｕｎｄｓ（ＬＸＸＩ）──ＳｏｌｉｄＳｔａｔｅＲｅａｃｔｉｏｎｓｏｆｏ－ＡｍｉｎｏｂｅｎｚｏｉｃＡｃｉｄｗｉｔｈＣｏｐｐｅｒ（Ⅱ）ＡｃｅｔａｔｅａｎｄＦｏｒｍ...     

无纺布上的偕胺肟基团鳌合物的氧化还原反应的研究

 采用各种分析方法系统研究了含偕胺肟基因维尼无纺布与Ａｎ³⁺进行氧化还原反应时的化学结构变化、氧化还原与鳌合吸附的关系以及还原产物的结晶结构和形态．结果表明，含偕胺肟基无纺布与Ａｕ³⁺反应时，开始主要是偕胺肟基被氧化成为酰胺基．此外，有部分偕胺基因被氧化成为羧基．Ａｎ³⁺被还原的同时生成约相等当量的氢离子．反应后期或反应温度高时，氢离子生成量增大．实验结果还表明，在反应起始阶段，Ａｕ³⁺与偕胺肟基因会发生鳌合作用．还原生咸的单质Ａｎ形成“玫瑰花”状的小晶粒粘附于无纺布纤维表面．     

还原温度对超细K－Co－Mo催化剂合成低碳醇性能的影响

 用溶胶－凝胶法合成了K－Co－Mo催化剂．样品经不同温度还原后，用于低碳醇的合成．XRD和HRTEM结果表明，样品是超细粒子，粒子尺寸为2～5nm．考察了催化剂的还原温度和反应条件对催化剂性能的影响．实验结果表明，还原温度对催化剂的活性有较大的影响，最佳还原温度为500℃．最佳反应温度范围为310～330℃．升高压力和空速可以提高醇的收率和选择性．在空速14400h－1，压力6．0MPa和温度310℃的条件下，醇的选择性为55．8％，收率为520．0g／（kg·h），MeOH／C2＋OH为0．27．催化剂稳定性良好，在200h的寿命实验中，活性基本不变．与文献中催化剂相比，超细K－Co－Mo催化剂对合成醇具有较高的活性和选择性，尤其是对C2＋OH的合成明显高于其他合成醇催化剂体系．     

α碘-α-甲氧羰亚甲基三苯胂的合成及其与芳醛的反应

胂叶立德分子中砷原子是以4 d 轨道稳定α-碳负离子,比相应的膦叶立德具有更强的亲核性,甲氧羰亚甲基三苯胂能与醛、酮顺利反应。因此,研究稳定的胂叶立德更具有合成     

苯与丙烯烷基化失活沸石催化剂氢再生机理

对工业中试用于苯与丙烯烷基化失活β－沸石改性催化剂进行了H2再生研究。通过对失活、新鲜和再生后催化剂的TPO、TPD、孔结构测定和活性评价以及失活和再生催化剂样品上炭组成的GC－MS分析，讨论了H2再生后催化剂催化性能的恢复状况。解释了虽然仍有部分炭未被除去，但酸性和活性恢复良好的原因。提出了本文体系失活催化剂H2再生过程的作用机理。     

Water/Oil Biphasic Hydroformylation of Higher Olefins over a TPPTS-Rh/SiO2 Catalyst

A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous highsurface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of mass transfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performance for hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of the traditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersed Rh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation of higher olefins such as 1-dodecene.     

3-N-丙酰基-2-芳基-5-(2-碘苯基)-1,3,4-噁唑啉类化合物的合成

2-碘苯甲酰肼与芳醛反应得到相应的酰腙(1),1再与丙酸酐脱水环化合成了3-N-丙酰基-2-芳基-5-(2-碘苯基)-1,3,4-噁唑啉类化合物,其结构经1H NMR,IR,MS和元素分析表征。     

Synthesis and Structure of a Dinuclear Copper（Ⅱ）- ditetrazolate Involving in situ Ligand Synthesis

The hydrothermal reaction of 1,2-dicyanobenzene with NaN3 in the presence of CuCl2, 2,2′-bipyridine and H2O affords a novel dinuclear copper(II)-ditetrazolate, [Cu(bpy)- (pdtz)]2 (Hpdtz = 5,5′-1,2-phenylene-ditetrazole, bpy = 2,2′-bipyridine). The pdtz ligand is generated in situ through Sharpless 2 3 cycloaddition reaction. Its crystal structure was deter- mined by single-crystal X-ray diffraction method. The crystal crystallizes in the monoclinic system, space group P21/n with a = 8.2096(16), b = 18.580(4), c = 11.838(2) , β = 103.12(3)o, V = 1758.5(6) 3, Z = 2, Mr = 863.83, Dc = 1.631 g/cm3, F(000) = 876 and μ = 1.272 mm-1. In this novel dinuclear structure, the pdtz ligand adopts a peculiar μ2-η1,η2 coordination mode.     

机械球磨与反应烧结合成Sr2CeO4发光体的研究

Sr₂CeO₄ phosphor was synthesized by mechanical milling and reactive sintering in this work. The solid state reaction of SrCO₃and CeO₂ (2∶1) started at about 850 ℃ and completed at 1 000 ℃ for about 4 h. Two types of formation mechanism of Sr₂CeO₄ were proposed. When the starting powder mixture was fired above 1 000 ℃, the unstable intermediate phase SrCeO₃was developed, which then reacted with SrCO₃to form the final product Sr₂CeO₄, however, SrCO₃and CeO₂ converted directly to Sr₂CeO₄ at a lower temperature. The XRD results showed the crystal structure of Sr₂CeO₄ was orthorhombic. The emission spectra displayed a broad band with maximum at about 465 nm. The mechanical milling of starting power mixture and the sintering temperature had no effect on this emission spectra.     

Studies of a new series of ion-pair complexes [Mo(dtc)_4][Ln(dtc)_4] (Ln=La-Er,exp.Pm)

A new series of ion-pair complexes [Mo(dtc)4][Ln(dtc)4] (Ln=La-Er, exp. Pm) were synthesized from MoCl5, LnCl3 and Nadtc in anhydrous methanol. The crystal structures of the four complexes, [Mo(dtc)4][Ln(dtc)4] (Ln=Nd, Sm, Ho and Er) have been determined by X-ray diffraction. Spectroscopic properties of all these complexes are also discussed here.