^31P NMR Studies on the Ligand Dissociation of Trinuclear Molybde-num Cluster Compounds

A series of carboxylate-substituted trinudear molybdenum dus-ter compounds formulated as Mo3S4(DTP)3(RCO2)(L), where RffiH, CH3, C2H5, CH2Cl, CCl3, R^1C6H4(R^1 is the group on the benzene ring of aromatic carboxylate ), L=pyridine,CH3CN, DMF, have been synthesized by the ligand substitu-tion reaction. The dissociation of the loosely-coordinated ligand L from the cluster core was studied by ^31p NMR. The dissocia-tion process of L is related to the solvent, temperature, and acidity of carboxylate groups, so as to affect the solution struc-ture and reactive properties of the duster. The long-distance in-teraction between ligands RCO2 and L is transported by Mo3S4 core.     

有机金属化合物中碳氢钼(锌)同时快速微量测定研究

由于某些有机金属化合物很不稳定,制取困难,获得量甚少,因此迫切需要建立相应的快速分析方法,并尽可能利用一份样品测出多种元素含量,以判断化合物的组成或纯度。虽然有机金属化合物(包括原子簇化合物)中碳、氢和金属的同时快速测定法已有报道,但是,某些有机钼(锌)化合物在高温燃烧氧化过程中,能生成挥发性的金属氧化物,并随着载气吹离样品舟,故不能简单地以高温氧化分解和称样品舟中残渣的方法来进行快速同时测定。本文对Gawargious等人建     

SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF IN-COMPLETE CUBANE CLUSTER C(MoCu_3S_3) (O)(μ-dtp)(PPh_3)_3]

<正> A new mixed-metal sulfido incomplete cubane cluster [(MoCuS3) (O) (μ-dtp) (PPh3)3] Cdtp = S2P (OC2H5)2] has been prepared by reaction of (NH4)2MoOS3 with Cu(dtp) (PPh3)2 in dimethylformamide solution. It crystallizes in the triclinic space group P1, a = 13.810(5), b = 19. 753(5), c=11. 719(4) A. α=99. 42(2), β=107. 24(3),γ=88. 05(3)°, V = 3012(2)A3, Dc = l. 51g/cm3and Z = 2. Final R=0. 046, Rw = 0. 056 for 7700 unique intensity data(I≥3σ(I)). The central unit [MoCu3S3]3+ can be described as a distorted incomplete cube with one missing corner. The Mo atom is tetrahedrally coordinated by three μ3-S atoms and one terminal O atom. Two Cu atoms are tetrahedrally coordinated whereas the third Cu atom has a highly distorted trigonal environment. The mean Mo - Cu bond length is 2. 752A. The Cu...Cu distances are in the range of 3. 200(1) -3. 740(1) A which are too long to form bonds.     

双二硫代乙酰丙酮二羰基铁的合成、晶体结构和分子结构

Fe(SacSac)_2(CO)_2晶体结构已用X射线衍射法测定,对于143t个I≥3σ(I)的衍射点最后偏离因子R=0.0056,R_w=0.058。分子结构基本特征是两个二硫代乙酰丙酮基及两个羰基成顺式构型,围绕Fe原子配位的4个S原子和2个C原子基本上成八面体。分子中的两个(SacSac)-配位基均是平面状的,C-C键长与通常的取代苯C-C键十分类似,均在1.37-1.38(?)之间。     

Synthesis and Crystal Structure of a Novel Hydrogen-Bonded Three-Dimensional Polymer [Zn(1,4-benzenedicarboxylate)-(pyridine)·H_2O]_n

ＩｎｔｒｏｄｕｃｔｉｏｎＤｅｓｉｇｎａｎｄｓｙｎｔｈｅｓｅｓｏｆｎｏｖｅｌｓｕｐｒａｍｏｌｅｃｕｌａｒｃｏｍ ｐｌｅｘｅｓｗｉｔｈｕｎｕｓｕａｌａｎｄｔａｉｌｏｒａｂｌｅｓｔｒｕｃｔｕｒｅｓａｒｅｆｕｎｄａ ｍｅｎｔａｌｓｔｅｐｓｉｎｄｉｓｃｏｖｅｒｙａｎｄｆａｂｒｉｃａｔｉｏｎｏｆｖａｒｉｏｕｓｔｅｃｈ ｎｏｌｏｇｉｃａｌｌｙｕｓｅｆｕｌｆｕｎｃｔｉｏｎａｌｓｕｐｒａｍｏｌｅｃｕｌａｒｄｅｖｉｃｅｓ .1 3Ｒｅｃｅｎｔｌｙ ,ｃｏｎｓｉｄｅｒａｂｌｅｅｆｆｏｒｔｓｈａｖｅｂｅｅｎｄｅｖｏｔｅｄｔｏｃｒ…     

OXIDATION DECARBONYLATION OF NH_4[Mo(CO)_5I]: SYNTHE-SES AND CRYSTAL STRUCTURES OF CMo(S_2CNC_4H_8)_4]I_3 · C_7H_8 and Mo_2S_2O_2(S_2CNC4H_8)_2

<正> Both of the title complexes were produced by oxidative decarbony-lation of NH4 CMO (CO)5I]. The complexes CMo(S2CNC4H8)4]I3 ?C7H8(1) and Mo2S2O2 (S2CNC4H8)2(2) both crystallize in triclinic, space group P1 with cell dimensions for (1) : a=13. 554(4), b=13. 620(4), c= 13. 058 (4) A , α=95. 58 (3), β=105. 38(2), γ=115. 49(2)°,V = 2035(1) A3, Z=2, Dc=1. 89 g. cm-3, final R=0. 054 and Rw = 0. 062 for 2926 observed reflections; and for (2): a = 8.730(2), b=16.592(6), c = 6. 688(2)A, α=97. 67(3), β=98. 10(2), γ=80. 26(2)% V = 939. 2(5) A3, Z = 2, Dc = 2. 05 g. cm-3, final R = 0. 038 and Rw = 0. 046 for 2248 observed reflections. The Mo(V) atom is bonded to eight S atoms in distorted dodecahedron for (1). The Mo atoms in compound (2) are bridged by two S atoms and each Mo atom is coordinated by two S atoms from S2CNC4H8 and one O atom to form distorted tetragonal pyramid.     

Synthesis and Characterization of ZnS∶Ag Nanocrystals Surface-capped with Thiourea

IntroductionSemiconductor nanocrystals(NCs) exhibit uniquechemical and physical properties due to their quantumsize effect and surface effect. Researches on synthesis,self-assembly, and fluorescent characteristics of thesemiconductor nanocrystals have rec…     

The role of W doping in response of hydrogen sensors based on MAO titania films

Anatase TiO₂ and W doped TiO₂ films were fabricated by micro-arc oxidation (MAO) on titanium substrates and their hydrogen sensing properties were investigated. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to characterize the oxide films and electrochemical impedance spectroscopy (EIS) was applied to investigate the gas sensing mechanism. It is found that the conductivity of TiO₂ films varies with the introduction of W dopant. EIS analysis reveals that the grains and especially the grain boundaries are mainly contributed to the hydrogen response and their equivalent circuits could be represented electrochemically by parallel resistor and constant phase element (CPE). The enhanced sensor signal at higher measuring temperature (300 °C) is observed with an optimal doping concentration of W ions (1.81 at.%).     

Superlinear Convergence of a Smooth Approximation Method for Mathematical Programs with Nonlinear Complementarity Constraints

<正>Mathematical programs with complementarity constraints(MPCC) is an important subclass of MPEC.It is a natural way to solve MPCC by constructing a suitable approximation of the primal problem.In this paper,we propose a new smoothing method for MPCC by using the aggregation technique.A new SQP algorithm for solving the MPCC problem is presented.At each iteration,the master direction is computed by solving a quadratic program,and the revised direction for avoiding the Maratos effect is generated by an explicit formula.As the non-degeneracy condition holds and the smoothing parameter tends to zero,the proposed SQP algorithm converges globally to an S-stationary point of the MPEC problem,its convergence rate is superlinear.Some preliminary numerical results are reported.     

塞曼石墨炉AAS法直接测定硝酸银中的杂质

本文介绍了利用塞曼石墨炉原子吸收法直接测定硝酸银中的杂质锰、镍、铜、铁和铬。方法简单、快速、检出限低、回收率好。