导电高聚物的EXAFS 研究(Ⅰ)铂氯酸(H2PtCl6·6H2O)掺杂的聚乙炔

在实验室EXAFS装置上测量了一种导电高聚物——H_2PtCl_6·6H_2O掺杂聚乙炔和模型化合物(K_2PtCl_6)的PtL_Ⅲ吸收谱。用高功率的施转阳极靶X射线发生器(RigakuRU-1000)作为X射线源。观测到的EXAFS数据分析表明, Pt原子在试样中有两种配位状态。一种是PtCl_6~(2-)离子, Pt—Cl键长为0.233 nm, 另一种是Pt在0.228 nm附近有两个最近邻的Cl原子。实验结果提供了支持下述观点的直接结构信息: 随着电子从(CH)_x链向铂盐的转移, 发生下列反应:2H_2PtCl_6+2e~-→PtCl_6~(2-)+PtCl_2+4HCl     

[(NH_3)_5CoImCu(dien)ImCo(NH_3)_5](ClO_4)_6·4H_2O配合物单晶的ESR研究

研究了咪唑桥联异三核配合物[(NH_3)_5CoImCu(dien)ImCo(NH_3)_5](ClO_4)_6·4H_2O与同构配合物[(NH_3)_5CoImZn(dien)ImCo(NH_3)_5]·4H_2O混合单晶在低温(100 K)下的ESR。应用适于求非同轴g张量和A张量的最小二乘法拟合技术,解出标题配合物的g张量和A张量主值分别为:g_1=2.246,g_2=2.093,g_3=2.048,A_1=1.63×10~(-2)cm~(-1),A_2=0.38×10~(-2)cm~(-1),A_3=0.17×10~(-2)cm~(-1)及g_1=2.245,g_2=2.090,g_3=2.051,A_1=1.64×10~(-2)cm~(-1),A_2=0.37×10~(-2)cm~(-1),A_3=0.17×10~(-2)cm~(-1)。配合物Cu~(2+)的4s、3d轨道上的电子自旋密度分别为0.018和0.557。Cu~(2+)与配体间的键有较强的共价性。     

四氯化铂与铂氯酸掺杂聚乙炔的X射线光电子能谱研究

用 X 射线光电子能谱法对四氯化铂(PtCl_4)及铂氯酸(H_2PtCl_6·6H_2O)掺杂聚乙炔进行了研究.发现Pt4f 与 Cl2p 谱峰均由相距约1.5eV 的两组峰组成.Pt4f 高结合能端的组份可指认为四价铂,而低结合能端的组份为二价铂.对 Pt4f 及 Cl2p 峰积分强度的分析表明,对二价铂有:[Cl]/[pt~(2 )]=2,对四价铂有:[Cl]/[pt4~ ]=6.C 1s 峰也由两个分离约1eV 的峰组成,高结合能端的强度随掺杂浓度的增加而增加.这些结果说明铂盐掺杂聚乙炔通过由高分子链向掺杂剂的电荷转移而使部份高分子链被氧化,部份四价铂盐被还原成 PtCl_2.透射电镜形态观察及选区电子衍射证明膜上存在 PtCl_2的聚集.电荷转移链段在高分子链上的分布是无规的.并由此估计了电荷转移链段上每个碳原子的电荷约为 0.2|e|.由以上结果我们推断 PtCl_4与 H_2PtCl_6·6H_2O 的电荷转移过程可由下式表达.对 PtCl_4 掺杂:2PtCl_4 2e→PtCl_6~(2-) PtCl_2对 H_2PtCl_6掺杂:2H_2PtCl_6 2e→PtCl_6~(2-) PtCl_2 4HCl这两种掺杂剂的对阴离子均是 PtCl_6~(2-)离子.     

异核金属簇合成及催化作用的研究——Ⅲ.从铂(Ⅳ)合成铂(Ⅱ)的膦络合物Pt[P(C_6H_5)_3]_2Cl_2

本文报道从高价铂(Ⅳ)络合物K_2PtCl_6和三苯基膦反应,一步合成Pt[P(C_6H_5)_3]_2Cl_2的新方法。根据副产物三苯基氧化膦(C_6H_5)_3PO的分离和鉴定,表明三苯基膦在反应中既是配位体,又是还原剂。     

前驱体水解对纳米铂形状控制合成的影响

以聚丙烯酸钠(NaPA: M_w ≈ 2100)为保护剂，对比研究了H_2还原K_2PtCl_4 和K_2PtCl_6水溶液制备纳米铂晶粒的形状选择性，揭示了前驱体的水解对纳米铂 晶粒的形状控制合成具有显著影响。文献中通常采用的合成立方形状纳米铂的 K_2PtCl_4前驱体在水溶液中不稳定，避光静置一周会析出黑色沉淀。这种不稳定 性导致了以K_2PtCl_4为Pt前驱体的合成结果难以重复。相比而言，避光静墨的 K_2PtCl_6水溶液很稳定，以它为前驱体合成的纳米铂通常为削角八面体。 K_2PtCl_6水溶液暴露于室内光线中会出现[PtCl_6]~(-2)的光致水解。当[PtCl_6] ~(2-)的紫外特征吸收峰(260nm)由于光致水解完全消失后，以聚丙烯酸钠为保护剂 ，通过H_2还原可以有选择性地(约80%)合成由{100}晶面包裹的立方体形状的纳米 铂。     

三硫氰酸根三乙二胺合镉(Ⅱ)钾(Ⅰ)的晶体结构

含钾和二价金属离子的双金属硫氰酸根配合物的晶体结构究研已有一些报道.在K_2Pb(SCN)~4和K_2Cd(SCN)_4·2H_2O这两个化合物中,晶体结构都是由K~+和M(SCN)_4~(2-)组成.本文报道了Cd(en)_3K(NCS)_3的晶体结构,其基本构型与上述两个化合物有显著的不同(en为乙二胺).     

1,1—环丙烷二羧酸根二氨合铂的晶体结构和振动光谱的简正坐标分析

测定了1,1-环丙烷二羧酸根二氨合铂([Pt(NH_3)_2CPrDCA]·H_2O)的晶体结构。晶体属正交晶系,空间群为Pnma,a=6.571(2),b=9.709(3),c=14.205(5)A,Z=4。用Patterson函数导出Pt原子坐标,经差值Fourier合成获得全部非氢原子坐标,用最小二乘法修正,最终R因子为0.058,采用U-B力场进行了[Pt(NH_3)_2CPrDCA]分子的简正坐标分析,振动基频的计算值与观测值符合,两者平均偏差5.63cm~(-1),最大误差15.7cm~(-1),证实了振动光谱的归属。     

顺铂与DNA结合方式——N_7、N_1链内交联模型化合物的合成和表征

以摩尔比为1:1的[Pt(NH_3)_2(H_2O)_2]·(NO_3)_2与鸟苷反应,经过重结晶,得到了1:1的纯化合物,通过摩尔电导、数均分子量、元素分析测定、~(13)CNMR、紫外光谱的表征,确定化合物为[{Pt(NH_3)2}_8(GuOH_(-1))_7(OH)_2]·(NO_3)_7·8H_2O。     

正八面体过渡金属化合物能谱的理论计算Ⅱ.

本文提出了在非限制Hartree-Fock方法计算的分子轨道基础上,计算分子价电子体系能谱和多电子状态的不可约张量方法。使用这种方法,计算了具有近似正八面体对称性的过渡金属化合物MnBr_6~(4-)、MnCl_6~(4-)、FeCl_6~(3-)、MnF_6~(4-)、Mn(H_2O)_6~(2+)、Co(NH_3)_6~(3+)、NiF_6~(4-)、Ni(H_2O)_6~(2+)、Ni(NH_3)_6~(2+)的d-d跃迁能谱。理论计算结果与实验符合较好,误差为若干k cm~(-1)     

高效液相色谱法研究铂(Ⅱ)配合物的配体交换反应

本文用高效液相色谱法研究了[Pt(TMDACP)I_2]和[Pt(TMDACP)(Cl-Ac)_2](TMDA是1,2,2-三甲基-1,3-二氨基环戊烷,Cl-Ac是氯乙酸根)的配体交换反应,测得20±0.1℃二级速率常数和平衡常数分别为(8.67±0.37)×10~(-3)mol~(-1)dm~3s~(-1)和0.572±0.008。     

Tetrathioureamercury(II) tetrathiocyanatomanganate(II)

In the title complex, [Hg(CH₄N₂S)₄][Mn(NCS)₄], the Hg and Mn atoms sit at special positions with symmetry and are tetrahedrally coordinated to four thio­urea (TU) S and four thio­cyanate (SCN) N atoms, respectively. The structure consists of discrete cationic and anionic [Hg(TU)₄]²⁺ and [Mn(SCN)₄]²⁻ complexes, and weak N_TU—H⃛S_SCN hydrogen-bond bridges exist between these complexes.     

Double Hydrated Cobalt(II) Copper(II) and Nickel(II) Copper(II) Ammine Diphosphates

Synthesis of amorphous and crystalline double hydrated cobalt copper and nickel copper ammine diphosphates with a coordination structure is described.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 3, 2005, pp. 369–372.Original Russian Text Copyright © 2005 by Voitenko, Zhilyak, Kopilevich.     

Eisen (II) und Kobalt (II)

Ohne Zusammenfassung     

Crystal structures of ethylenediaminecadmium(II) tetracyanocadmate(II)-benzene(1/2) and ethylenediaminecadmium(II) tetracyanocadmate(II)

The crystal structure of ethylenediaminecadmium(II) tetracyanocadmate(II)-benzene(1/2),I, has been redetermined based on 1632 reflections collected anew for the crystal coated with epoxy resin, with a final conventionalR=0.038;I crystallizes in space groupP4₂22, witha=b=8.265(1) andc=15.512(3) Å, andZ=2. Ethylenediaminecadmium(II) tetracyanocadmate(II),II, is concluded to be identical with the residual metal complex host ofI, remaining after the liberation of the guest benzene molecules;II crystallizes from an aqueous solution containing bis- or tris-ethylenediaminecadmium(II) tetracyanocadmate(II) in space groupI4₁/acd, witha=b=14.366(1) andc=23.771(4) Å, andZ=16; refinement led to a conventionalR=0.043 for 1181 reflections. The bridging ethylenediamine ligand inI turns to a chelating one inII; dissociation and recombination should occur in the coordination sphere of the six-coordinate cadmium atom, whenII is derived fromI by the liberation of the guest molecules. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82018 (30 pages).Dedicated to Professor H. M. Powell.     

Cadmium(II), manganese(II) and zinc(II) compounds

Three new compounds, [Cd(μ ₃ -Hpdh)(μ₂-Cl)] _n (1), Mn(Hpdh)₂(H₂O)₂ (2) and Zn(Hpdh)₂ (H₂O)₂ (3) (H₂pdh =?pyridine-2,3-dicarbo-2,3-hydrazide), have been synthesized and characterized by elemental analysis, IR spectra, TG and single-crystal X-ray diffraction. Under hydrothermal conditions, H₂pdh is generated by an in situ acylation of H₂pda (H₂pda =?pyridine-2,3-dicarboxylic acid) with hydrazine hydrate. Complex 1 features a 2D layer structure constructed by a dinuclear Cd(II) building block. In complexes 2 and 3, hydrogen bonding interactions connect mononuclear structures into 3D supramolecular frameworks.     

Hexaaquacobalt(II) bis(hypophosphite) and hexaaquacobalt(II)/nickel(II) bis(hypophosphite)

The title compounds, hexa­aqua­cobalt(II) bis­(hypophosphite), [Co(H₂O)₆](H₂­PO₂)₂, and hexa­aqua­cobalt(II)/nickel(II) bis(hypophosphite), [Co_0.5Ni_0.5(H₂O)₆](H₂PO₂)₂, are shown to adopt the same structure as hexa­aqua­magnesium(II) bis­(hypophosphite). The packing of the Co(Ni) and P atoms is the same as in the structure of CaF₂. The Co^II(Ni^II) atoms have a pseudo‐face‐centred cubic cell, with a = b～ 10.3 Å, and the P atoms occupy the tetrahedral cavities. The central metal cation has a slightly distorted octahedral coordination sphere. The geometry of the hypophosphite anion in the structure is very close to ideal, with point symmetry mm2. Each O atom of the hypophosphite anion is hydrogen bonded to three water mol­ecules from different cation complexes, and each H atom of the hypophosphite anion is surrounded by three water mol­ecules from further different cation complexes.     

Electrophilic Copper(II) → Metal(II) Substitution in Gelatin-Immobilized Copper(II) Hexacyanoferrate(II) Matrix Implants

Contact of thin layers of gelatin-immobilized copper(II) hexacyanoferrate(II) matrices with aqueous solutions of Co(II), Ni(II), Zn(II), and Cd(II) chlorides results in partial substitution of these ions for Cu(II) to give (dd)-heterobinuclear hexacyanoferrates(II) of copper(II) and the corresponding double-charged ion.     

Magnetic,epr and SOD studies of some Cu(II)-Cu(II), Cu(II)-Ni(II) and Cu(II)-Zn(II) imidazolate bridged complexes

Magnetic, spectroscopic and superoxide dismutase activity of imidazolate bridged [(Salala)Cu-Im-Cu(Salala)]Na, [(Salala)Cu-Im-Zn(Salala)]Na and [(Salala)Cu-Im-Ni(Salala)]Na (Salala=Salicyledenealiniate, Im=Imdiazolate) are described. The epr and electronic spectra of related mononuclear complexes, viz., [(Salala)Cu-OH(2)] and [(Salala)Cu-ImH] also described. Appearance of a half-field signal in polycrystalline and decrease in mu(eff) per copper(II) ion indicate super exchange coupling between copper(II) ion in [(Salala)Cu-Im-Cu(Salala)]Na binuclear complex. A pH-dependent epr and UV-vis study of 50% aqueous DMSO solution of binuclear complexes suggest that the complexes are stable in narrow pH range.