共查询到20条相似文献,搜索用时 0 毫秒
1.
2.
3.
S. V. Korenev Yu. V. Shubin S. A. Gromilov I. A. Baidina T. V. Basova 《Journal of Structural Chemistry》2002,43(4):643-648
Monohydrates of chloropentammine rhodium(III) and chloropentammine cobalt(III) tetracloropalladates(II) were synthesized. Single crystals of [Rh(NH3)5Cl][PdCl4] · H2O were obtained and studied by Xray diffraction. The crystallographic data are as follows: a = 7.8730(16) Å, b = 10.905(2) Å, c = 16.038(3) Å, = 102.70(3)°, V = 1343.3(5) Å3, space group P21/c, Z = 4, dcalc = 2.422 g/cm3. The structure consists of alternating layers of [Rh(NH3)5Cl]2+ complex cations and [PdCl4]2- complex anions. Each anion layer contains two crystallographically independent Pd atoms, and the square coordination environment of one of these atoms is converted to a bipyramide. The structure of the compound [Co(NH3)5Cl][PdCl4] · H2O is determined and its unitcell parameters are refined: a = 7.813(3) , b = 10.896(4) , c = 15.966(5) , = 102.85(4)°, V = 1325.2(8) 3, and dcalc = 2.148 g/cm3. The synthesis temperature is shown to have an effect on the content of hydrated and anhydrous complexes in the mixture formed during precipitation of these binary salts from aqueous solutions. 相似文献
4.
采用水热法合成了一个钨-钒簇聚物[Cu(en)2]2[VⅤ{Cu(en)2(H2O)}2]·3H2O(1, en=乙二胺), 并通过X射线单晶衍射、 元素分析、 傅里叶变换红外光谱、 X射线粉末衍射、 热重分析、 价键计算、 X射线光电子能谱、 电子顺磁共振和磁性分析对其结构和性能进行了表征. 结果表明, 化合物1是以双支撑的四帽Keggin结构 [(VⅤO4){Cu(en)2(H2O)}2]4- 钨-钒簇合物阴离子为基本结构单元, 与4个[Cu(en)2]2+配合物阳离子以共价键和弱键相连接形成二维层状结构, 相邻层又通过氢键连接成三维超分子网络. 研究了化合物1的磁性及光催化降解罗丹明B的活性. 相似文献
5.
T. N. Fedotova G. G. Aleksandrov G. N. Kuznetsova 《Russian Journal of Inorganic Chemistry》2008,53(12):1862-1869
The Platinum(II) diamine with N,N-dimethylethylenediamine (N,N-dimeEn) [Pt{(CH3)2N(CH2)2NH2}Cl2] (I) was synthesized. The reaction of the diamine with pyridine gave Pt(II) tetramine [Pt{(CH3)2N(CH2)2NH2}Py2]Cl2 (II), which was oxidized with chlorine to give Pt(IV) triamine Pt{[(CH3)2N(CH2)2}PyCl3]Cl · H2O (III). The reaction of III with chlorine (chloroamidation) yielded chloroimide [Pt{(CH3)2N(CH2)2NCl}PyCl3] (IV). The IR spectra of complexes I–IV and UV/Vis spectra of III and IV were studied. X-Ray diffraction analysis was performed for III (monoclinic crystals, space group P21/c, a = 7.7437(6), b = 8.1100(7), c = 28.52992(2) Å, β = 93.7280(10)°, Z = 4, R hkl = 0.0420) and IV (orthorhombic crystals, space group Pna21, a = 15.7825(12), b = 7.4447(6), c = 12.3099(6) Å, Z = 4, R hkl = 0.0539). During oxidation of Pt(II) tetramine with chlorine, the pyridine molecule is removed from the cis position relative to the (CH3)2N group (trans position relative to the NH2 group) of N,N-dimethylethylenediamine. The reaction of chloroimide complex IV with concentrated HCl (dechloroamidation) at 20°C afforded the initial complex III; that at 100°C, gave triamine III together with Pt(IV) diamine [Pt(N,N-dimeEn)Cl4] (V) (monoclinic crystals, space group P21/n, a = 7.1278(5), b = 11.5384(8), c = 12.7501(9) Å, β = 93.23(10)°, Z = 4, R hkl = 0.0239). 相似文献
6.
T. N. Fedotova G. G. Aleksandrov G. N. Kuznetsova 《Russian Journal of Inorganic Chemistry》2010,55(7):1026-1036
Treatment of platinum(II) diamine [Pt(N,N-DimeTm)Cl2] (I) with pyridine gave tetramine [Pt(N,N-DimeTm)Py2]Cl2 (II); by oxidation with chlorine this was converted to Pt(IV) triamine, [Pt“(N,N-DimeTm(Py)Cl3]Cl (III) with a six-membered chelate ring. According to X-ray diffraction data, the reaction of complex II with chlorine is accompanied by removal of the pyridine molecule from the trans-position to the NH2 group of N,N-dimethyltrimethylenediamine. The reaction of complex III with chlorine at 20°C afforded a mixture of compounds (IV) and the complex [Pt“(CH3)2N(CH2)2C(O)NH”(Py)Cl3] (V) with an amidate six-membered metal ring, dimethylpropioamide, which was also isolated upon refluxing a mixture of IV in an aqueous solution. The UV/Vis and IR spectra of the obtained complexes were studied, and X-ray diffraction analysis of I, III, and V was performed. The crystals of I are triclinic, space group P $ \bar 1 $ ; a = 7.6526(4) Å, b = 11.5571(6) Å, c = 12.4432(7) Å, α = 113.85(1)°, β = 96.54(2)°, γ = 106.78(2)°; Z = 4; R hkl = 0.051. The crystals of III are monoclinic, space group C2/c; a = 36.715(2) Å, b = 7.8179(4) Å, c = 29.721(16) Å, β = 127.80(1)°; Z = 16; R hkl = 0.036. The crystals of V are monoclinic, space group P21/n; a = 7.0398(6) Å, b = 27.458(2) Å, c = 7.687(6) Å, β = 106.270(1)°; Z = 4; R hkl = 0.052. 相似文献
7.
采用密度泛函理论B3LYP方法, 在B3LYP/6-311++G(2d,2p)//B3LYP/6-311++G(d,p)基组水平上对乙醇-水分子团簇(C2H5OH(H2O)n (n=1-9))的各种性质进行研究, 如: 优化的几何构型、结构参数、氢键、结合能、平均氢键强度、自然键轨道(NBO)电荷分布、团簇的生长规律等. 结果表明, 从二维(2-D)环状结构到三维(3-D)笼状结构的过渡出现在n=5的乙醇-水分子团簇中. 此外, 利用团簇结合能的二阶差分、形成能、能隙等性质, 发现在n=6时乙醇-水分子团簇的最低能量结构稳定性较好, 可能为幻数结构. 最后, 为了进一步探讨氢键本质, 将C2H5OH(H2O)n (n=2-9)最低能量结构的各种性质与纯水分子团簇(H2O)n (n=3-10)比较, 结果表明前者与后者中的水分子之间氢键相似. 相似文献
8.
采用从头算Hartree-Fock(HF),M??ller-Plesset微扰(MP2),二级近似耦合簇(CC2)和密度泛函理论(DFT)方法,对IB族金属-乙烯配合物LM-C2H4(L=[N{(Me)C(Ph)N}2];M=Cu,Ag,Au)的几何结构、电子结构以及LM与C2H4之间的结合能进行了理论研究.MP2、CC2和密度泛函方法对C2H4配位前后C=C键长的变化情况都给出了正确的描述.电子结构分析显示LM与C2H4之间主要以C2H4→LM"σ-给予"和LM→C2H4"π-反馈"方式协同成键,这种成键方式使C2H4配体π轨道上的电子密度下降,π*轨道上的电子密度增加,并使得C=C键长增加、键能下降,从而达到活化C=C键的目的.自然电荷布居和能量分解分析显示LM-C2H4中的"σ-给予"作用弱于"π-反馈"作用,若使用"σ-给予"作用强于"π-反馈"作用的M+-C2H4体系作为LM-C2H4的简化模型进行理论研究是不合适的.LM-C2H4中金属原子M的改变对C=C键长、C2H4电荷布居以及LM与C2H4之间的结合能等性质影响显著.LAu与LCu、LAg相比其接受和反馈电子的能力最强,使C2H4配体π轨道电子密度减少的程度和π*轨道电子密度增加的程度也最大,因此LAu对C2H4中C=C键的活化效果最好.螯合配体取代基供、吸电能力的改变对上述性质的影响则非常有限. 相似文献
9.
K3[GdⅢ(nta)2(H2O)]·6H2O和(NH4)·[GdⅢ(Cydta)(H2O)2]·5H2O的合成及晶体结构 总被引:3,自引:0,他引:3
GdⅢ的配合物常被用作MRI造影剂[1,2]. GdⅢ的离子半径和电子结构分别为0.107 8 nm和高自旋f 7, 理论预测应与氨基多羧酸类配体形成稳定的九配位配合物[3~5]. 为证实理论预测并在此基础上寻找合适的可用于定向修饰的配体以及为提高GdⅢ配合物的脂溶性使其具有更好的细胞渗透性, 选择四齿配体nta和含有脂环烃的六齿配体Cydta分别合成了GdⅢ的配合物, 并测定了它们的分子结构. 结果显示, GdⅢ与nta形成九配位配合物, GdⅢ与Cydta形成八配位配合物. 相似文献
10.
《Journal of organometallic chemistry》1986,316(3):325-333
The protonated species [Fe2(η-C5H5)2(CO)2(η-CO){μ-CN(Me)H}]X, [Fe2(η-C5H5)2(CO)(CNMe)(μ-CO){μ-CN(Me)H}][X], and [Fe2(η-C5H5)2(CO)2{η-CN(Me)H}2][X]2 react with one equivalent of AgY. The Ag+ and one H+ act together as a two-electron oxidant. Silver metal is precipitated quantitatively and the substrates cleaved to give mono-nuclear products of the type (a) [Fe(η-C5H5)(CO)(L)X] and [Fe(η-C5H5(CO)(L)Y] or (b) Fe(η-C5H5(CO)(L)(CNMe)][X] (L = CO, CNMe). If X− and Y− are both coordinating anions such as NO3−, I−, or Br− or the solvent is MeCN products of type (a) are usually obtained with X = Y = MeCN+ if acetonitrile is used as the solvent. However, if either X− or Y− is a non-coordinating anion such as BF4− or PF6− and methanol is the solvent, the products are usually those of type (b). When X− = [p-MeC6H4SO3]−, both types of products are obtained in significant amounts. If two equivalents of Ph3P are added to the methanol solution of [Fe2(η-C5H5)2(CO)2{-CN(Me)H}2[BF6]2, no reaction takes place until the third equivalent of AgNO3 has been added. The products have been isolated and characterized by analysis and infrared spectroscopy. The previously unreported [Fe2(η-C5H5)2(CO)(CNMe)(η-CO){η-CN(Me)H}] X salts are described for X− = BF4−, PF6−, Br− · 2H2O, I− · H2O, NO3− · 0.5H2O, and p-MeC6H4SO3−. 相似文献
11.
Cluster coordination polymer {(n-Bu4N)2[Mo2O2S6Cu6Br4(4,4'-bipy)3]·0.5H2O)}n (4,4'-bipy=4,4'-bipyridine),has been synthesized and characterized by X-ray crystallography. The polymeric anion {[Mo2O2S6Cu6Br4(4,4'-bipy)3]2-}n is composed of secondary building units (SBUs) [MoOS3Cu3], Br atoms and 4,4'-bipy ligands. Two secondary building units [MoOS3Cu3] and a double parallel 4,4'-bipy ligands form an octanuclear rectangular metallamacrocycle with the dimension of 1.13×0.39 nm2, which is further connected by single bridging 4,4'-bipy ligands to form a 1D zigzag structure. Crystal data for compound 1: C62H97N8O2.50S6Br4Cu6Mo2,M=2 079.68, Triclinic, P1, a=0.982 40 (10) nm, b=1.293 70(10) nm, c=1.737 4(2) nm, α=97.810(10)°,β=101.390(10)°,γ=108.520(10)°, V=2.005 1(4) nm3, Z=2, Dc=1.722 g·cm-3, F(000)= 1039,μ (Mo Kα)=4.055 mm-1, the final R=0.040 7, wR2=0.097 2. CCDC: 236407. 相似文献
12.
13.
将1,4-二氮杂二环[2.2.2]辛烷(DABCO)、 二水合氯化铜和盐酸溶于甲醇-水混合溶剂中, 通过常温蒸发法制备了一个新颖的无机-有机杂化化合物[(H2DABCO)CuCl4]·H2O(1). 利用红外光谱(IR)、 X射线粉末衍射(XRD)、 单晶X射线衍射、 元素分析、 热重分析(TG)、 变温-变频介电分析等对化合物1进行结构表征及性质测试. 在低温(100 K)和室温(294 K)下, 该化合物属于单斜晶系P21/c空间群, 在bc平面内, 通过N—H…O, O—H…Cl等氢键自组装作用形成二维网状结构. 而铜离子在c轴上的相对位移导致化合物1在多轴方向呈现出明显的开关型介电异常峰, 变温-变频介电常数沿不同晶轴呈显著的各向异性. 相似文献
14.
《Journal of Coordination Chemistry》2012,65(8):969-983
Preparation of the ammonium salt of TPPMS, [NH4]TPPMS, TPPMS = PPh2(m-C6H4SO? 3), greatly enhances water solubility and provides an efficient route to other metal complexes of TPPMS, M(TPPMS)2 M = Mn2+, Co2+, Fe2+ and Ni2+. For Co2+ and Fe2+ the metal has an octahedral ligand environment with five water molecules and one TPPMS coordinated through the sulfonate oxygen; the second TPPMS is not coordinated. For Ni2+ the octahedral coordination sphere is composed of water molecules and the TPPMS ligands are not coordinated. Structures are fully reported for [NH4]TPPMS·½H2O and [Fe(H2O)5(TPPMS)]TPPMS and partially reported for [Co(H2O)5TPPMS]TPPMS and [Ni(H2O)6]TPPMS2·H2O. All of the structures show hydrophobic regions consisting of aromatic rings and hydrophilic regions with hydrogen-bonding interactions. 相似文献
15.
16.
于中温水热条件下合成出一种三维亚磷酸铁(H3O)2·[FeⅡ5(HPO3)6], 并对其进行了单晶解析、热重及磁性等系列表征. 晶体属三方(Trigonal)晶系, P3c1空间群, a=1.026 9(5) nm, b=1.026 9(5) nm, c=0.929 5(6) nm, Z=2. 化合物中心铁原子采取略变形八面体构型, 与亚磷酸根假四面体连接形成三维骨架结构, 沿c轴方向有一六元环孔道. 相似文献
17.
The title compound[Zn(btzb)2Cl2]·2H2O(1·2H2O,btzb=1,2-bis(5-tetrazolyl)benzene)was synthesized in situ by the[2 3] cycloaddition reaction of phthalonitrile with NaN3 in water in the presence of ZnCl2 under refluxing conditions.1·2H2O crystallizes in the monoclinic system,space group P21/c with a=9.0119(18),b=7.5566(15),c=18.076(5)(A),β=114.67(2)°,V=1118.6(4)(A)3,Z=2,Dc=1.784 g/cm3 T=223(2)K,C16H16N16O2Cl2Zn,Mr=600.74,F(000)=608,μ(MoKα)=1.393 mm-1,S=1.081,R=0.0306 and wR=0.0669 for 1896 observed reflections with Ⅰ >2σ(Ⅰ).The Zn2 ion of 1 is coordinated by four N atoms from two btzb ligands and two Cl atoms,forming a distorted octahedral coordination geometry.A number of intermolecular hydrogen bonding interactions between molecules 1 and/or the solvated water molecules result in a 3D hydrogen-bonded structure.The luminescent property of 1·2H2O was also investigated. 相似文献
18.
Kou Hui-Zhong Gao Dong-Zhao Bu Wie-Ming Fan Yu-Guo Liao Dai-Zheng Cheng Peng Jiang Zong-Hui Yan Shi-Ping Wang Geng-Lin Li Tian-Jian Tang Jin-Kui 《Transition Metal Chemistry》2001,26(4-5):457-460
Two CrIII–FeIII complexes, K2[Cr(salen)(H2O)][Fe(CN)6]·H2O (1) and [trans-Cr(tn)2Cl2]3[Fe(CN)6]·6H2O (2), have been prepared. Crystal structure determination shows that complex (2) possesses an ionic salt structure. General physical measurements and magnetic studies indicate that (1) assumes a cyanide-bridged dinuclear structure, and that the CrIII–FeIII magnetic coupling through the cyanide bridge is antiferromagnetic, which can be rationalized by the overlap of magnetic orbitals of the same symmetry. 相似文献
19.
应用ABEEM/MM力场模型研究水分子团簇(H2O)n(n=7~35)的性质 总被引:1,自引:1,他引:0
应用ABEEM/MM模型研究和计算了水分子团簇(H2O)n(n=7~35)的各种性质,如:优化的几何构型,氢键个数,结合能,稳定性,ABEEM电荷分布,偶极矩,以及结构参数、平均氢键个数和强度、团簇的递增结合能等,并描述了六聚水区域中所反映的从二维结构(从二聚水到五聚水)到三维结构(n>6的水分子团簇)的过渡,又进一步地预测了从立方体结构到笼状结构的过渡出现在n=12的水分子团簇中,随着类似于笼状结构特点的不断增强,五元环的富集程度有所增加.以上研究不仅系统研究和分析了水团簇的各种性质,而且对比Ab initio研究和实验结果,进一步验证了ABEEM/MM模型的合理性以及参数的正确性和可转移性. 相似文献
20.
采用水热合成法以丁二胺作为模板剂合成了钴的有机二膦酸超分子化合物[NH3(CH2)4NH3]Co(hedpH2)2(H2O)2 [hedpH4 = 1-羟亚乙基二膦酸, CH3C(OH)(PO3H2)2]。用元素分析、红外光谱、紫外-可见光谱、热重分析以及单晶结构解析对其进行了表征。该化合物的化学式为:C8H30N2CoO16P4,Mr = 593.15,晶体属单斜晶系,空间群C2/c,晶胞参数a = 16.128(2), b = 12.427(1), c = 12.610(2) ? b = 121.389(9), V = 2157.3(4) 3, Z = 4, Dc = 1.826 g/cm3, m(MoKa) = 1.172 mm-1, F(000) = 1228。结构用直接法解出,最终偏离因子R = 0.0285, wR = 0.0747。该化合物的结构包含单核的Co(hedpH2)2- 阴离子,阴离子之间通过氢键连结形成具有空隙的三维超分子骨架结构,双质子化的丁二胺分子位于空隙中。 相似文献