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1.
新型簇合物(n-Bu4N)2「Fe4S4(tpbt)4」(tpbt-2,4,6-三苯基苯硫酚基)通过2,4,6-三苯基苯硫酚和(n-Bu4N)2「Fe4S49S-t-Bu04」在DMF中进行配体交换反应合成得到。该簇合物在CH3CN溶液中的「Fe4S4」^3+/2+和「Fe4S4」^2+1/+的氧化还原电位分别为-0.14和-1.31VvsSCE。 相似文献
2.
簇合物〔WOS3Cu3(γ-pic)6〕Br(C36H42BrON6S3Cu3W, Mr= 1125.34) 属于三方晶系,空间群为P3,晶胞参数为:a= 12.264(5), c= 15.905(8) , γ= 120.00°, V=2071(2)3, μ(MoKα)= 5.490m m - 1, Z= 2, Dc= 1.804g/cm 3, F(000)= 1104 , R= 0.052 , w R= 0.053. 可观察衍射点1901 (I≥2σ(I))。该簇合物的分子由游离的阴离子Br- 和簇阳离子〔WOS3Cu3(γ-pic)6〕+ 构成。阳离子中的W 原子、S原子和Cu原子构成1 个巢状骨架结构,且该结构中存在一个通过W 和O原子的C3 轴。 相似文献
3.
室温或近室温条件下,2-氨基嘧啶(AP)与4种铜(Ⅱ)盐CuCl2.2H2O,CuBr2,CuSO4.5H2O,CuAc2,H2O发生固-固相化学反应,生成3类不同配位比(Cu/AP)分别为2:2、1:1和1:2)的2-氨基嘧啶合铜与合物,用元素分析,碘量法,电感耦合等离直读光谱、IR、XRD、UV、ESR等方法表征了固相反应产物,不同阴离子铜盐的结构是影响固相反应的主要原因。讨论了固相反应的过程 相似文献
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三核钼簇Mo3S4(dtp)4.HO21(dtp=S2P(OC2H5)2)和对甲基苯磺酸反应,以C2H5OH做为介质,在CdCl2和PPh3参预下获得新颖的三核簇合物Mo(μ3-S)(μ-S)3-(μ-CH3C6H4SO3)(dtp).(C2H5OH)2.本文报导化合物2的晶体结构、红外光谱、紫外光谱研究结果。簇合物的分子结构存在一个非络合物的对甲基苯左侧酸基和两个Mo的桥式络合,颇为罕见。而簇分 相似文献
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利用CS2与镉硫化合物在溶剂中反应产生S^2-来合成大核镉硫簇合物,得到了两个新的大核镉硫簇合物,并测定了其晶体结构,化合物(Ⅰ)为(Me4N)2[SCd8(SPh)12Cl4],晶体属立方晶系,空间群Pa3,a=26.782(3)A,V=19211(4)A^3,Dc=1.750g/cm^3,Z=8.1637个衍射点参与修正,R=6.96%,化合物(Ⅱ)为[Cd(H2O)6][SCd8(SPh)1 相似文献
7.
室温下[Et_4N]_2MoSe_4, FeCl_2和 R_2NCS_2Na在 DMF和 CH_3CN混合溶剂中反应,得到含MoFe_3Se_4核芯的Mo-Fe-Se簇合物MoFe_3Se_4(μ-R_2NCS_2)_2(R_2NCS_2)_4(R2=Me_2(1),Et_2(2),C_4H_8(3)).化合物2的单晶X射线衍射分析表明,其分子结构为2个桥式和4个螫合Et_2NCS_2~-配体包围的一个扭曲类立方烷M_4Se_4簇核对3个化合物的CV进行了表征,它们在DMSO溶液中的电化学行为表现出了多电子可逆的传递过程. 相似文献
8.
标题固相合成V—Cu—S簇合物;VS4(CuPPh3)5X2(X=Br,I)的晶体结构 总被引:1,自引:0,他引:1
标题两个化合物是在反应体系(NH4)3VS4/CuX/PPh3/NEt4X中采用低温固相反应方法得到的,单晶X射线结构分析表明:VS4(CuPPh3)5Br2(I)和VS4-(CuPPh3)5I2是同构的,其中晶体属于单斜晶系,空间群P21c,Mr=1968.2,a=20.215(7),b=15.691(4),c=27.345(9)A,β=95.29(3)°,V=8637.0A^3,Z=4,Dc= 相似文献
9.
室温或近室温条件下,2-氨基嘧啶(AP)与4种铜(Ⅱ)盐CuCl_2·2H_2O、CuBr_2、CuSO_4·5H_2O、CuAc_2·H_2O发生固-固相化学反应,生成3类不同配位比(Cu/AP分别为2:2、1:1和1:2)的2-氨基嘧啶合铜配合物。用元素分析、碘量法、电感耦合等离子直读光谱(ICP)、IR、XRD、UV、ESR等方法表征了固相反应产物。不同阴离子铜盐的结构是影响固相反应的主要原因。讨论了固相反应的过程。反应沿晶格结构变化最小(活化能最低)的途径进行。 相似文献
10.
由(NH4)2WS4,AgI和Bu4NBr用低热温固相反应合成了类立方烷簇合物<Bu4N>3.<WAg3S4I4>。用X射线单晶衍射法测定其晶体结构。 相似文献
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The reaction system (NH4)3VS4/CuCl/PPh3/Et4NBr afforded a series of [VS4-Cun] dusters with various core configurations in the solid state at low heating temperature. The structural regularity of [VS4-Cun] dusters and the influence of the CuCl:(NH4)3VS4 ratio as well as that of reaction temperature and time on the formation of duster core have been summarized. The reaction mechanism of forming V-Cu-S clusters has also been explored. 相似文献
12.
《Polyhedron》1999,18(8-9):1339-1343
The complexes containing [VS4–Cun] (n=3, 4, 5, 6) clusters were characterized by NMR spectra. The relationship between the 51V NMR chemical shift and the number of copper atoms in a cluster was established. 51V NMR chemical shifts were used to identify possible products of the reactions of Cu(PPh3)Cl and [VS4–Cu3] with various mole ratios in CDCl3 in order to study their reaction mechanism in solution. The results demonstrate that the reaction of tetranuclear [VS4–Cu3] and Cu(PPh3)Cl in CDCl3 successively yields penta-, hexa- and hepta-nuclear V–Cu–S heterometallic clusters when the mole ratio of [VS4–Cu3] to Cu(PPh3)Cl is decreased, and the process can be reversed when [VS4–Cu3] is added to [VS4–Cu6] gradually. Theoretical calculations were also carried out to explain the experimental results. 相似文献
13.
Anangamohan Panja Sanchita Goswami Nizamuddin Shaikh Partha Roy Mario Manassero Ray J. Butcher Pradyot Banerjee 《Polyhedron》2005,24(18):2921-2932
The reaction of copper chloride dihydrate and ferric chloride hexahydrate with a tripodal N4 ligand (ntb) under mild conditions affords two novel complexes [Cu(ntb)Cl]2[CuCl4] · 2H2O (1) and [Fe(ntb)Cl2]Cl · 3H2O (2). The reaction of ferric chloride with another N4 ligand, bispicpn, forms an octahedral mononuclear complex, [Fe(bispicpn)Cl2]Cl (3). Single-crystal X-ray structural studies of 1, 2 and 3 reveal the formation of hydrogen-bond sustained 3D, 2D and 1D networks, respectively, involving (N–HO) and (N–HCl) interactions. The packing arrangement in 2 further reveals the existence of hexagonal channels with helical propagation along the diagonal of the crystallographic b- and c-axes. The reactions of these complexes with 3,5-di-tert-butylcatechol have been studied in dimethylformamide. NMR techniques have been used to identify the reaction products. 相似文献
14.
Aapo U. Hrknen Markku Ahlgrn Tapani A. Pakkanen Jouni Pursiainen 《Journal of organometallic chemistry》1997,530(1-2):191-197
Three tetranuclear clusters [Ru4H4(CO)11(PPh3)] (1), [Ru4H2(CO)12(PPh3)] (2) and [Ru3IrH(CO)12(PPh3)] (3) were formed in the reaction of [Ir(CO)Cl(PPh3)2] and Na[Ru3H(CO)11] in tetrahydrofuran. Complexes 1–3 were characterized by IR and 1H and 31P NMR, and the structure of the clusters was confirmed by single crystal X-ray analysis. In 2 and 3 one of the carbonyls bridges between two ruthenium atoms; otherwise the compounds contain only terminal carbonyls. 相似文献
15.
标题两个化合物是在反应体系(NH4)3VS4/CuX/PPh3/NEt4X(X=Br,Ⅰ)中采用低温固相反应方法得到的,单晶X射线结构分析表明:VS4(CuPPh3)5Br2(Ⅰ)和VS4-(CuPPh3)5I2(Ⅱ)是同构的,其中晶体(Ⅰ)属于单斜晶系,空间群P211/c,Mr=19682,a=20.215(7),b=15.691(4),c=27.345(9)A,β=95.29(3)°,V=8637.0A3,Z=4,Dc=1.51g/cm3,F(000)=3968,μ(MoKa)=24.6cm-1,R=0.078。晶体(Ⅱ)亦属于单斜晶系,Mr=2062.2,空间群P21/c,a=20.1613(2),b=15.9718(2),c=27.7427(3)A,β=96.07(1)°,V=8883.4A3,Z=4,Dc=1.54g/cm3,F(000)=4112,μ(MoKa)=22.0cm-1,R=0.068。簇合物(Ⅰ)和(Ⅱ)的簇芯结构可描述为共面的2个开口的扭曲立方烷,在这两个簇合物中,V原子仍保持反应起始物[VS4]3-中的四面体配位,5个CU原子呈近似的四方锥排列,V原子基本上处于Cu5四方锥底面的中心。其中1个Cu原子为平面三角形配位,另外4个Cu原子为严重畸变的四面体配位。 相似文献
16.
Ashraf A. Aly Esam A. Ishak Ahmed M. Shwaky Asmaa H. Mohamed 《Monatshefte für Chemie / Chemical Monthly》2020,151(2):223-229
Quinoline-2,4-diones reacted with 2-[bis(methylthio)methylene]malononitrile in DMF/Et3N to produce 3-(methylthio)-4-oxo-4,5-dihydrofuro[3,2-c]quinolone-2-carbonitriles and 3-(methylthio)-4-oxo-4,5-dihydrofuro[3,2-c]quinolone-2-carboxamides in state of 2-imino-substituted 4-(methylthio)-5,6-dihydro-2H-pyrano[3,2-c]quinolone-3-carbonitriles. The structures of all new products were proved using NMR, IR, and mass spectral data. The possible mechanism for the reaction is also discussed. 相似文献
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Cubane-type clusters [Fe(4)S(4)(SR*)(4)](2-) containing chiral thiolate ligands with R* = CH(Me)Ph (1), CH(2)CH(Me)Et (2), and CH(2)CH(OH)CH(2)OH (3) have been prepared by ligand substitution in the reaction systems [Fe(4)S(4)(SEt)(4)]/R*SH (1-3, acetonitrile) and [Fe(4)S(4)Cl(4)](2-)/NaSR*(3, Me(2)SO). Reactions with successive equivalents of thiol or thiolate generate the species [Fe(4)S(4)L(4-n)(SR*)(n)](2-) (L = SEt, Cl) with n = 1-4. Clusters 1 and 2 were prepared with racemic thiols leading to the possible formation of one enantiomeric pair (n = 1) and seven diastereomers and their enantiomers (n = 2-4). Reactions were monitored by isotropically shifted (1)H NMR spectra in acetonitrile or Me(2)SO. In systems affording 1 and 2 as final products, individual mixed-ligand species could not be detected. However, crystallization of (Et(4)N)(2)[1] afforded 1-[SS(RS)(RS)] in which two sites are disordered because of occupancy of R and S ligands. Similarly, (Et(4)N)(2)[2] led to 2-[SSSS], a consequence of spontaneous resolution upon crystallization. The clusters 3-[RRRR] and 3-[SSSS] were obtained from enantiomerically pure thiols. Successive reactions lead to detection of species with n = 1-4 by appearance of four pairs of diastereotopic SCH(2) signals in both acetonitrile and Me(2)SO reaction systems. Identical spectra were obtained with racemic, R-(-), and S-(+) thiols, indicating that ligand-ligand interactions are too weak to allow detection of diastereomers (e.g., [SSSS] vs [SSRR]). The stability of 3 in Me(2)SO/H(2)O media is described. 相似文献
18.
Beves JE Constable EC Housecroft CE Neuburger M Schaffner S Shardlow EJ 《Dalton transactions (Cambridge, England : 2003)》2007,(16):1593-1602
The reaction of 4'-(2-propyn-1-oxy)-2,2':6',2'-terpyridine (HC[triple bond]CCH2Oterpy) with trans-[PtI2(PR3)2] (R = Et, (n)Bu, Ph) results in the regioselective formation of the metalloditopic ligands trans-[Pt(C[triple bond]CCH2Oterpy)2(PR3)2], crystallographic data for which are presented. Each ditopic ligand reacts with FeCl(2).4H(2)O to give heterometallomacrocycles, the smallest of which is a [2 + 2] macrocycle, confirmed structurally for R = Et. The NMR spectroscopic data confirm the formation of symmetrical species, i.e. macrocyclic and not polymeric species. The distribution of products has been investigated using pulsed-field gradient spin-echo (PGSE) diffusion NMR spectroscopy, and indicates that the kinetic products from the reactions of 1, 2 or 3(L) with iron(II) are [Fe(n)L(n)](2n+) with n = 2, 3 or 4. For L = 1 and 2, these mixtures of products convert in solution to the thermodynamically favoured [Fe(2)L(2)](4+). 相似文献
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The synthesis, reactivities, spectroscopic, electrochemical, and structural studies of copper(I), copper(II), nickel(II), and cobalt(II) complexes of 6,6'-bis(bromomethyl)-2,2'-bipyridine (bpy-Br2) and 6,6'-bis(chloromethyl)-2,2'-bipyridine (bpy-Cl2) have been reported. The copper(I) complex [CuI(bpy-Br2)2](ClO4) (1) has been obtained in two crystallographic modifications, in which the coordination geometry of the metal center has the D2d symmetry. The reaction between CuCl2.2H2O and bpy-Br2 has been followed spectrophotometrically at 45 degrees C over a period of 7 h, and a mechanism for the intramolecular halogen exchange and scrambling in the initially formed compound [CuII(bpy-Br2)Cl2] (5) has been proposed. Depending upon the reaction conditions, several halogen-exchanged products, namely [CuII(bpy-Br1.86Cl0.14)(Cl1.89Br0.11)] (2), [CuII(bpy-Br1.81Cl0.19)(Cl1.70Br0.30)(H2O)] (3), and [CuII(bpy-Br0.63Cl1.37)(Cl0.54Br1.46)] (4), have been isolated in crystalline form. The reaction between bpy-Cl2 and CuCl2.2H2O provides [CuII(bpy-Cl2)Cl2] (7) and [CuII(bpy-Cl2)Cl2(H2O)] (8), whereas CoCl2.6H2O and NiCl2.6H20 on reaction with bpy-Br2 under boiling condition produce [CoII(bpy-Br0.5Cl1.5)(ClBr)] (11) and [NiII(bpy-Br0.46Cl1.54)(Cl0.73Br1.27)(H2O)] (12), respectively. The X-ray structures determined for the 4-coordinate compounds 2, 4, and 7 show flattened tetrahedral geometry for the metal center with the D2 symmetry. Both 5-coordinate compounds 3 and 12 have square pyramidal geometry, and whereas the nickel(II) complex 12 has near-perfect geometry (tau = 0.015), considerable distortion is observed for the copper(II) complex 3 (tau = 0.25). Complexes [CuII(bpy-Cl2)Br2] (6) and [CuII(bpy-Br2)Br2] under boiling condition undergo photoreduction to produce the dimeric copper(I) complexes [{CuI(bpy-Cl1.30Br0.70)(mu-Br)}2](9) and [{CuI(bpy-Br2)(mu-Br)}2] (10), respectively. The fact that the photoreduction of [CuII(bpy-Cl2)Br2] (6) and [CuII(bpy-Br2)Br2] do not take place in absence of light has been established by spectrophotometric measurements. The crystal structures of 9 and 10 have been determined. The electrochemical behavior of all the copper complexes 1-10 has been studied in acetonitrile and dichloromethane. The E1/2 values for the CuI/CuII redox couples show strong solvent dependence and for a given system the E1/2 value is more positive in dichloromethane relative to that in acetonitrile. For the compounds [CuII(bpy-Br2-xClx)(Cl2-yBry)] (x = 0-2, y = 0-2), the E1/2 values become more positive with the increase of y value. 相似文献