共查询到20条相似文献,搜索用时 15 毫秒
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杂核金属含硫簇合物具有丰富的结构,在生物化学、催化和非线性光学等方面显示了诱人的应用前景.近年来,我们主要从事用[MS4 ]2 - 和[Cp* MS3]- ( M=Mo,W)和Cu( ) ,Ag( )反应合成Mo( W) /Cu( Ag) /S簇合物并研究其非线性光学性质[1,2 ] .鉴于用硫代金属酸盐作前驱体合成M- Cu- Ag- S杂三核金属簇合物的工作鲜有报道[3] ,我们尝试用( NH4 ) 2 Mo OS3和Cu Br,Ag Br在α- Me Py中反应,希望得到Mo- Cu- Ag- S杂三核金属簇合物.但上述反应却形成了1个仅含Mo和Cu( )的五核簇合物[Mo OS3Cu4 (α- Me Py) 6 Br2 ],其所含的Mo S3… 相似文献
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Reactions of (NH4)2MS4, AgBr and CuBr in γ-methylpyridine produced one new compound, [MS4Cu4(γ-MePy)8][M6O19] (1, M = W; 2 , M = Mo), of which 1 was characterized by single crystal X-ray analysis. The crystal data: orthorhombic, Pbcn, a = 15.434(4), b = 16.732(2), c = 28.657(7) Å, V = 7400.8(8) Å3, Z = 4 , R = 0.072 for 3121 independent data. The compound is the first example which contains both polyoxotungstate anion and heteropolynuclear cluster cation. In the structure of the cation four edges of the tetrahedral WS2?4 core are coordinated by four copper atoms, giving a WS4Cu4 aggregate of approximate D2h symmetry. The differences between the reaction of Cu+ with MS2?4 and that of Ag+ with MS2?4 in pyridine and its derivatives are discussed. 相似文献
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Reactions between thiomolybdate or thiotungstate [Et4N]2[MS4] (M = Mo, W) and CuSBut led to the formation of two novel Mo(W)/Cu/S clusters [Et4N]4[{MS4Cu2(μ-SBut)}4] (1, M = Mo; 2, M = W). Single-crystal X-ray diffraction studies reveal that 2 is the first example of a molecular square containing CuS2WS2Cu building blocks. The reactions of [Et4N]2[MS4] with CuCl followed by the addition of K2SSS (SSS = 1,3,4-thiadiazole-2,5-dithiolate) yielded novel polymers {[Et4N]2[MS4Cu2(SSS)]}n (3, M = Mo; 4, M = W). Crystal structure determination shows that the CuS2WS2Cu building blocks in the anion of 4 are bridged by SSS2− ligands to produce a helical chain running down the crystallographic b axis. 相似文献
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LI Jian-Rong LIN Ping LI Zhi-Hua DU Shao-Wu 《结构化学》2009,28(11):1475-1479
The self-assembly reactions of [MOS3]^2- (M = W, Mo) with CuS2COCH3 in DMF produced two novel dodecanuclear Mo(W)/Cu/S heterometallic clusters, [Et4N]4[{MOS3}3Cu6S2- (CuS2COCH3)3]·H2O (1: M = W; 2: M = Mo). Cluster 1 crystallizes in hexagonal, space group P-62c with a = 16.5612(3), b = 16.5612(3), c = 16.4660(5)A, Z = 2, V = 3911.13(16)A^3, Dc = 1.935 g/cm^3, μ(MoKα) = 7.269 mm^-1, F(000) = 2192, the final R = 0.0289 and wR = 0.0789 for 2425 observed reflections (I 〉 2σ(I)). Cluster 2 is isomorphous to 1 with similar crystal parameters. X-ray analysis reveals that both clusters consist of three incomplete cubane-like cluster units {MOS3Cu3S2COCH3}, which are linked together by two μ3-S atoms. 相似文献
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Four novel M/Cu/S polymers [Et4N][MS4Cu3(S2COEt)2] (1a: M=Mo; 1b: M=W) and Et4N][MS4Cu2SEt] (2a: M=Mo; 2b: M=W) have been prepared by reactions of [Et4N]2[MS4] with CuS2COEt and CuSEt. X-ray crystal structure determinations reveal that the polymeric anions of complexes 1a and 1b both consist of MS4Cu3 building blocks linked via bidentate [S2COEt]− bridging ligands to form 1D polymeric chains. The anion structures of the polymeric compounds 2a and 2b contain MS4Cu2 repeating units which are connected via μ-SEt− ligands forming a zigzag chain running down the crystallographic b axis. 相似文献
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合成了四个三核簇合物[A]2[MS4(CuCN)2](1A=Et4N,M=Mo;2A=PPh4,M=W;3A=Et4N,M=W;4A=PPh4,M=Mo),测定了[Et4N]2[MoS4(CuCN)2]*H2O(1*H2O)和[PPh4]2[WS4(CuCN)2]*0.5DMF*H2O(2*0.5DMF*H2O)的晶体结构.1和2的簇阴离子[MS4(CuCN)2]2-(M=Mo,W)均具有一个双齿配体MS42-和两个CuCN形成的近似D2d对称性结构. 相似文献
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一维链状配位聚合物{[Cu(H2bttc)(H2O)3]·3H2O}n的非等温反应动力学和晶体结构 总被引:1,自引:0,他引:1
为研究配位聚合物{[Cu(H2bttc)(H2O)3]·3H2O}n(H2bttc=1,2,4,5-benzenetetracarboxylate)的热分解机理和非等温反应动力学进行了DSC和TG-DTG热分析。由热分析结果和FTIR光谱推测了其热分解机理;将Kissinger法、Ozawa法、积分法和微分法得到的动力学参数进行比较确定了第一个失重过程最可能的动力学模型函数。配位聚合物的X射线单晶结构分析表明它由 [Cu(H2bttc)(H2O)3]n分子链组成,并有客体水分子通过分子间氢键附着在分子链上。这一结构特点与热分析结果相一致。还有一种氢键将分子链连接起来形成二维框架,这一框架在失去配位水和结晶水后到553 K开始分解。 相似文献
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Xin Bo ZHOU Cui Fang LIN Song LI 《中国化学快报》2005,16(10):1301-1304
The synthesis of (S)-2-(3-arylacrylamido)-3-{4-[2-(5-methyl-2-phenyloxazol-4-yl)etho- xy]phenyl}propanoic acids is described. Their structures were confirmed by ^1H-NMR. 相似文献
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本文设计合成了两种以聚吡唑硼酸盐、吡唑为配体的铜配合物Cu2[ μ-pz]2[HB(pz)3]2(1)和Cu[B(pz)4]2(2)(pz:吡唑(C3H4N2))。运用元素分析、红外光谱对配合物进行了表征,并用X-ray衍射测定了它们的晶体结构。非等温热分解动力学研究表明:配合物1的热分解反应分两步,配合物2的热分解反应一步进行。通过计算,配合物1热分解的第一步反应的可能机理为成核与生长,n=1/4;第二步反应的可能机理为化学反应。其非等温动力学方程分别为:dα/dT=A/β e-E/RT·1/4(1-α)[-ln(1-α)]-3和dα/dT=A/β e-E/RT·(1-α)2。分解反应的表观活化能分别是520.37 kJ·mol-1和149.65 kJ·mol-1;指前因子lnA分别是118.06 s-1和28.10 s-1。配合物2热分解的可能机理为化学反应。其非等温动力学方程为:dα/dT=A/β e-E/RT·(1-α)2。分解反应的表观活化能是111.41 kJ·mol-1;指前因子lnA是21.20 s-1。 相似文献
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《Journal of Coordination Chemistry》2012,65(16):2515-2527
In a search for environmentally friendly metal chelating ligands for industrial applications, the protonation and complex formation equilibria of [S,S,S]- and [R,S,R]-isomers of N-bis[2-(1,2-dicarboxyethoxy)ethyl] aspartic acid (BCA6) with Mg(II), Ca(II), Mn(II), Fe(III), Cu(II) and Zn(II) ions in aqueous 0.1 M NaCl solution were studied at 25°C by potentiometric titration. The model for complexation and the stability constants of the different complexes were determined for each metal ion using the computer program SUPERQUAD. With all metal ions (M n+), stable ML n?6 complexes dominated complex formation for both isomers. Differences in complexation models were found for binuclear species. 相似文献
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Masahiro Yuki Masaaki Okazaki Shinji Inomata Hiroshi Ogino 《Angewandte Chemie (International ed. in English)》1998,37(15):2126-2128
Thermal and photochemical interconversion occurs between the isomeric pair of tetrathiotungstate [WS4]2− clusters 1 and 2 , which were formed by thermolysis of [Cp*2Ru2S4] and [W(CO)3(MeCN)3] [Eq. (1)] and then structurally characterized. During synthesis, a dramatic redistribution of ligands between the Ru and W atoms takes place without the loss of any CO and S ligands. 相似文献
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In our working toward the rational design and synthesis of cluster-based supramolecular architectures, a set of new [WS4Cu4]- or [MoOS3Cu3]-based supramolecular assemblies have been prepared from reactions of preformed cluster compounds [Et4N]4[WS4Cu4I6] (1) and [(n-Bu)4N]2[MoOS3Cu3X3] (2, X = I; 3, X = SCN) with flexible ditopic ligands such as dipyridylsulfide (dps), dipyridyl disulfide (dpds), and their combinations with dicyanamide (dca) anion and 4,4'-bipy. The cluster precursor 1 reacted with dps or dpds and sodium dicyanamide (dca) in MeCN to produce [WS4Cu4I2(dps)3].2MeCN (4.2MeCN) and [WS4Cu4(dca)2(dpds)2].Et2O.2MeCN (5.Et2O.2MeCN), respectively. On the other hand, treatment of 2 with dpds in DMF/MeCN afforded [MoOS3Cu3I(dpds)2].0.5DMF.2(MeCN)0.5 (6.0.5DMF.2(MeCN)0.5) while reaction of 3 with sodium dicyanamide (dca) and 4,4'-bipy in DMF/MeCN gave rise to [MoOS3Cu3(dca)(4,4'-bipy)1.5].DMF.MeCN (7.DMF.MeCN). Compounds 4.2MeCN, 5.Et2O.2MeCN, 6.0.5DMF.2(MeCN)0.5, and 7.DMF.MeCN have been characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray crystallography. Compound 4 contains a 2D layer array made of the saddle-shaped [WS4Cu4] cores interlinked by three pairs of Cu-dps-Cu bridges. Compound 5 has another 2D layer structure in which the [WS4Cu4] cores are held together by four pairs of Cu-dca-Cu and Cu-dpds-Cu bridges. Compound 6 displays a 1D spiral chain structure built of the nido-like [MoOS3Cu3] cores via two pairs of Cu-dpds-Cu bridges. Compound 7 consists of a 2D staircase network in which each [MoOS3Cu3(4,4'-bipy]2 dimeric unit interconnects with four other equivalent units by a pair of 4,4'-bipy ligands and two pairs of dca anions. The [WS4Cu4] core in 4 or 5 and the [MoS3Cu3] core in 7 show a planar 4-connecting node and a seesaw-shaped 4-connecting node, respectively, which are unprecedented in cluster-based supramolecular compounds. The successful assembly of 4-7 from the three cluster precursors 1-3 through flexible ditopic ligands provides new routes to the rational design and construction of complicated cluster-based supramolecular arrays. 相似文献
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1 INTRODUCTION The catalytic asymmetric synthesis has been a challenging subject in organic synthesis. The deve- lopment of efficient enantioselective catalysts appli- cable to a wide range of carbon-carbon bond form- ing reactions represents a pivotal … 相似文献
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A. Müller A. Hildebrand E. Krickemeyer D. Slter H. Bgge A. Armatage 《无机化学与普通化学杂志》1992,614(8):115-120
(PPh4)[(ReO2S2)CuI] and (NEt4)2[ReOS3)Cu3Cl4]: Fixation of the up to now not Isolated Ions [ReO2S2]? and [ReOS3]? Utilizing the Stability of the CuS2(Re) and Cu3S3(Re) Fragments (PPh4)[(ReO2S2)CuI] ( 1 ) and (NEt4)2[ReOS3)Cu3Cl4] ( 2 ) containing the up to now not isolated oxothioperrhenate ions [ReO2S2]? and [ReOS3]? as ligands, have been prepared by the reaction of (NEt4)[ReS4] with PPh3 and CuI in acetone in the presence of (PPh4)I (( 1 )) or with CuCl in CH2Cl2 in the presence of (NEt4)Cl (( 2 )), respectively. 1 and 2 have been characterized by X-ray structure analysis, elemental analysis and spectroscopic studies (IR, UV/Vis). The electronic spectra show bands which can approximately be assigned to interesting low-energy charge-transfer-transitions of the type d(Cu) → d(Re). For crystal data see Inhaltsübersicht. 相似文献