新型富勒烯膦金属配合物的合成

用配体取代法合成了新型富勒烯膦金属配合物——C60.双(二苯基膦)戊烷合钯[C60Pd(dpppe),1],其结构经UV-Vis,IR,XPS及元素分析表征。在1的分子结构中,C60以σ-π配位方式与Pd配位,形成新型的η2-C60双齿膦金属配合物。     

含双二苯基膦甲烷铜(Ⅰ)配合物的研究进展

本文概述了含双二苯基膦甲烷铜(Ⅰ)配合物的化学进展,总结了配合物的合成方法:置换法、还原法、电化学方法和直接加成法,全面论述了双核、三核、多核和异核配合物的结构特征,探讨了该类配合物的重要荧光性质。     

含双二苯基膦甲烷四核铜(Ⅰ)配合物的合成

室温合成了含双二苯基膦甲烷 (dppm)的四核铜 (Ⅰ)配合物 [Cu4 (C7H4 NO4 ) 2 (dppm) 4](NO3) 2(C7H4 NO4 为 2 ,6 二羧酸吡啶 ) ,研究了配合物的物理化学和光谱性质 ,晶体属三斜晶系 ,空间群P 1 ,a =1 .2 592 ( 3) ,b =1 .4 1 87( 4) ,c =1 .70 38( 3)nm ;α =1 0 2 .54( 2 ) ,β =95.4 1 ( 2 ) ,γ =90 .33( 2 )°;V =2 9567( 2 )nm3,Dc=1 .2 95g·cm-3 ,Z =1 ,R =0 .0 5472 ,Rw=0 .0 6773。     

含双二苯基膦乙烷镍配合物的合成与性质

在氯访中通过取代反应制备了含双二苯基膦乙烷（ｄｐｐｅ）的镍配合物［Ｎｉ（ｄｐｐｅ）Ｃｌ_２］,并通过元素分析、热分析、红外光谱、核磁、电导测定、光电子能谱及Ｘ－射线单晶分析表征了配合物的结构和性质,晶体属于单斜品系,空间群为ｐ２_１／ｃ。晶胞参数如下：ａ＝１１．４２９（２）,ｂ＝１３．３４６（２）,ｃ二１５．９５３（７）Ａ;β＝９９．１３（３）°,Ｖ＝２４０２．５Ａ~３, Ｚ＝４, Ｆ（０００）＝１０８８, Ｄ_（ｃａｌｃ）＝１４６０９· ｃｍ~（－３）, ｐ＝１１．７８２ｃｍ~（－１）, Ｒ＝０．０４４７０, Ｒｗ＝０．０５３５２。分析结果表明,配合物中双二苯基膦乙烷属双齿配体,氯离子是单齿配体．     

含双二苯基膦甲烷双核铜Ⅰ配合物的合成及性质

利用配体取代反应合成了四种含双二苯基膦甲烷(dppm)的双铜(Ⅰ)配合物[Cu₂(dppm)₂L₂](NO₃)₂(配体L分别是2,2'-联吡啶(1)、邻菲咯啉(2)、2,9-二甲基-邻菲咯啉(3)、吡啶(4)],并经核磁、热分析、光电子能谱等方法表征了配合物的性质。配合物(1)的晶体结构显示,dppm作为桥式双齿配体、联吡啶作为双齿配体分别与铜原子形成四面体配位结构,硝酸根离子位于配合物外界。     

富勒烯的金属配合物及其催化性能

富勒烯的金属配合物及其催化性能１）刘英陈远荫２）盛蓉生（武汉大学化学系武汉４３００７２）关键词富勒烯金属配合物催化分类号Ｏ６４３．３２碳元素的第三种存在形式富勒烯正以其独特的结构和性能以及诱人的应用前景引起人们日益浓厚的兴趣．其中又以Ｃ６０的研究为主...     

C60Pt(BINAP)金属配合物的合成表征与光电性能研究

本文利用配体取代法合成了C60Pt(BINAP)新型富勒烯膦金属配合物,采用质谱、元素分析、紫外.可见吸收光谱、红外吸收光谱、光电子能谱等对该产物进行了表征,并测定了其在光化学电池中的光伏效应.光伏效应测试结果表明:在BQ/H2Q与I2/I3-介质溶液中镀层厚度为1～2μm时,具有较好的光电转换性能,光生电压值最高达358 mV.     

聚硅氧烷负载富勒烯铂配合物的合成及其催化性能

对 C60 及其衍生物的金属化合物催化性能的研究表明 ,以富勒烯为基体的催化剂对许多化学反应具有独特的催化活性 ,这方面的研究是富勒烯科学的一个重要发展方向 ,并显示出良好的应用前景 .但在已有的工作中 ,研究的主要是 C60 的小分子金属配合物、有机金属复合物以及纳米级金属吸附在C60 的表面所形成的金属 - C60 混合物等的催化性能 ,而有关高分子负载富勒烯金属配合物在催化方面的应用较少报道 [1～ 5] .富勒烯是一个具有独特球形 π电子体系的弱电子给体 ,且体积庞大 ,它的引入势必会改变高分子负载催化剂金属活性中心的局部电荷密度…     

含双(2-二苯基膦苯基)醚的Ag(Ⅰ)配合物的合成和表征

合成了2个含有双膦配体的Ag（Ⅰ）配合物,分别是[Ag（DPEphos）（dppe）]₂SO₄（1）和[Ag（DPEphos）（SCN）]₂·CH₂Cl₂（2）（DPEphos=双（2-二苯基膦苯基）醚,dppe=双（二苯基膦）乙烷）,并通过红外光谱,核磁氢谱,元素分析,X射线单晶衍射及荧光光谱表征分析。通过热重分析了2个配合物的热稳定性。结构分析表明配合物1具有简单的单核结构,每个Ag和2个膦配体中的4个P原子螯合配位。配合物2具有双核结构,在配合物2中存在微弱的金属与金属间的作用。在Ag₂S₂环中,4个原子相互之间形成的内角之和为360°,形成的环[-Ag-S-Ag-S-]是一个平行四边形。荧光光谱显示配合物中的发射峰主要来源于双膦配体中的π-π^*跃迁。热重分析结果表明,在340℃附近,2个配合物开始分解,具有良好的稳定性。     

双（二苯基膦）丁烷的双核银配合物晶体结构

报导了双（二苯基膦）丁烷的双核银配合物－［Ａｇ（Ｐｈ_２ＰＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２ＰＰｈ_２）－（ＮＯ_３）］_２的合成及晶体结构分析。晶体属于单斜晶系，空间群为Ｐ２_１／ｎ，晶胞参数为：ａ＝１２．８２１（３），ｂ＝１１．２４４（９），ｃ＝１９．３８６（９），β＝１０５．９４（３）°，Ｖ＝２６８７．２~３，Ｚ＝２，Ｄ_ｃ＝１．４７４ｇ／ｃｍ~３，Ｍ_ｒ＝１１９２．７，Ｆ（０００）＝１２１６，μ＝８．８７３ｃｍ~（－１）。晶体结构由直接法和Ｆｏｕｒｉｅｒ合成解出，使用对角块矩阵和全矩阵最小二乘法对原子参数进行修正，最后偏离因子Ｒ＝０．０５６，Ｒ_ｗ＝０．０６８，其中２６３４个Ｉ＞３σ（Ⅰ）的可观察点参加了结构修正，单晶结构分析结果表明，在该配合物中，配体双（二苯基膦）丁烷（ｄｐｐｂ）中的磷原子直接与银离子配位，硝酸根也以双齿配位形式存在，中心银离子的配位采用畸变的四面体构型，整个分子是一个二聚物。     

Synthesis and Crystal Structure of a Tetranuclear Silver Complex with Bis（diphenylphosphino） amine-dioxide as a Tridentate Ligand

1 INTRODUCTION The coordination chemistry of the nitrogen-contai- ning diphosphine ligand bis(diphenylphosphino)ami- ne (Ph2PNHPPh2) has recently received much atten- tion because the P atoms can bridge metal centers in μ-bonding mode to form bi- or polynuclear complex- es[1~10]. It has been shown that the acidity of N–H proton would promote functionalization on the ligand backbone[4, 5, 11]. Although a few complexes contain- ing deprotonated tridentate Ph2PNPPh2 have been synthesi…     

Coordination Triangular Prism of Bisilver Complex with Triply—bridged of Bis（diphenylphosphino）amine

1 INTRODUCTION Recently coinage metal complexes of poly- dentate phosphines are of great interest owing to the applications in diverse areas such as supramolecular design, photophysics and catalysis[1～4]. It is well- known that the binuclear coinage metal complexes of diphosphine [M2(diphosphine)2(MeCN)2]2+ (M = Cu, Ag, Au)[5～16] are excellent precursors for the design of polynuclear or polymeric materials with desired properties due to the easy substitution of weakly coordinated ac…     

Triply-bridged Dicopper(Ⅰ)Complex of Bis(diphenylphosphino)acetylene with a Helical Coordination Cage

<正>Self-organization of copper (I) ion with bridging ligand bis(diphenylphosphino)-acetylene resulted in the isolation of a dinuclear copper ( I ) complex [Cu2(μ-Ph2PC≡ CPPh2)3(MeCN)2](ClO4)2·Et2O. Structural analysis indicated the existence of a helical coordination cage, in which two copper (I) atoms are bridged triply by the linear diphosphine Ph2PC≡CPPh2 with the CuACu separation of 6.231 A. The copper (I) atom is in an approximately tetrahedral environment with a NP3 coordination chromophore. The complex crystallizes in the triclinic, space group P 1 with a = 13.8456(2), b = 16.6010(1), c = 18.9215(3) A, α = 98.289(1), β = 91.232(1), γ = 106.496(1)°, V = 4117.60(9) A3, Z = 2, C86H82Cl2N2O9P6Cu2, Mr= 1659.37, Dc= 1.338 g/cm3, F(000) = 1708, μ = 0.754 mm-1, the final R = 0.0688 and wR = 0.1940 for 11692 reflections with I>2σ(I).     

Heterotetranuclear CuI2PdⅡ2 Complex with Bis(diphenylphosphino)methane and Diethyldithiocarbamate

Self-assembly between the building blocks of Pd(Et2dtc)2 (Et2dtc = diethyldithio carbamate) and [Cu2(μ-dppm)2(MeCN)2]2+ (dppm = bis(diphenylphosphino)methane) gave a new heterotetranuclear complex [Cu2Pd2(μ-dppm)2(μ-Et2dtc)2(μ3-Et2dtc)2](ClO4)2.H2O (C70H86Cl2Cu2-N4O9P4Pd2S8, Mr = 1932.56), and its crystal structure has been determined by X-ray crystallography. It crystallizes in triclinic, space group P1- with a = 11.9834(6), b = 12.5624(6), c =14.5603(8) A, α = 101.393 (1), β = 103.300 (1), γ= 96.310(1)°, V = 2063.2(2) A3, Z = 1, Dc =1.544 g/cm3,μ(MoKα) = 1336 cm-1 and F(000) = 978. The total and unique reflections are 8710 and 5400, respectively. The structure was refined to R = 0.0860 and wR = 0.1996 for 3914 observed reflections with I ＞ 2σ(Ⅰ). The title complex consists of the cation [Cu2Pd2(μ-dppm)2(μ-Et2dtc)2(μ3-Et2dtc)2]2+, anion ClO4- and solvate H2O. The Pd(Ⅱ) atoms are located at the approximately square-planar environments with PS3 donors and the Cu(Ⅰ) atoms display distorted tetrahedral geometries.     

Heterotetranuclear Cu_2~IPd_2~Ⅱ Complex with Bis(diphenylphosphino)methane and Diethyldithiocarbamate

1 INTRODUCTION The design of heterometallic complexes of photoluminescnece is of current interest for the inorganic chemists[1, 2]. The coordination flexibility of -dppm ligand as well as the easy substitution of weakly coordinated solvate donors by stronger donors makes the binuclear compound [M2(m- dppm)2(sol)2]2+ excellent building block for con- structing various molecular materials with desired properties[3～5]. We are devoted to developing heterometallic photoluminescent transitio…     

Preparation and Characterization of Trimethylsilylpyridylacetylene Bridged,Dicobalt Carbonyl Complexes Containing Bis(diphenylphosphino)methylene or Bis(diphenylphosphino)ethylene Ligand

Reaction of an alkyne‐bridged dicobalt complex, [Co₂(CO)₆(μ‐Me₃SiC=Cpy)] 4 , with bis(diphenylphosphino)methylene (DPPM) or bis(diphenylphosphino)ethylene (DPPE) in THF at 55 °C yielded a DPPM or DPPE doubly bridged dicobalt compound, [{μ‐P,P‐PPh₂CH₂PPh₂}Co₂(CO)₄(μ‐Me₃SiC=Cpy)] 5 or [{μ‐P,P‐PPh₂CH₂CH₂PPh₂}Co₂(CO)₄(μ‐Me₃SiC≡Cpy)] 6 . Compound 5 and 6 were characterized by spectroscopic means as well as X‐ray crystal structure determination.     

Synthesis and properties of the chain-like polymeric copper (II) complexes bridged by bis(diphenylphosphino oxide)ethane

At room temperature, the chain-like polymeric copper (II) complexes bridged by bis (diphenylphosphino oxide) ethane (dppeO2), [Cu(dppeO2)X2]n[X=Cl(1), Br(2)] have been prepared and characterized by elemental analysis, 31P NMR, TG-DTA and X-ray analysis for [ CuBr2 (dppeO2) ] n The chain is composed of subunits containing tetrahedron coordinated copper (II) atoms. The four-coordinated copper (II) atom is ligated to another four-coordinated copper (II) atom through dppeO2. The coordination sphere of copper(II) atom is completed by two monodentate bromide and two oxygen atoms from bridging dppeO2. Crystal data are as follows: C26-H24CuP2BnO2, 0.50 mm× 0.40 mm×0.40 mm, monoclin-ic, space group: C2/c, λ= 0.07107 nm(Mo Ka), a = 1.2286(2) nm, b=2.0555(8) nm, c = 1.0652(2) nm, β = 97.366(9)°, V = 2.668nm3, Z = 4, Dcalc = 1.628 g·cm-3, R = 0.066; Rw = 0.091.     

Rhodium(I) carbonyl complexes of mono selenium functionalized bis(diphenylphosphino)methane and bis(diphenylphosphino)amine chelating ligands and their catalytic carbonylation activity

The chelate complexes of the types (1) and (2) have been synthesized and characterized by IR and NMR spectroscopy. The lower shift of the ν(P-Se) bands and downfield shift of the ³¹P-{¹H}NMR signals for both P(III) and P(V) atoms in 1 and 2 compared to the corresponding free ligands indicate chelate formation through selenium donor. 1 and 2 show terminal ν(CO) bands at 1977 and 1981 cm⁻¹, respectively, suggesting high electron density at the metal center. The molecular structure of 2 has been determined by single-crystal X-ray diffraction. The rhodium atom is at the center of a square planar geometry having the phosphorus and selenium atoms of the chelating ligand at cis-position, one carbonyl group trans- to selenium and one chlorine atom trans- to phosphorus atom. 1 and 2 undergo oxidative addition (OA) reaction with CH₃I to produce acyl complexes (3) and (4), respectively. The kinetics of the OA reactions reveal that 1 undergoes faster reaction by about 4.5 times than 2. The catalytic activity of 1 and 2 in carbonylation of methanol was higher than that of the well known species [Rh(CO)₂I₂]⁻ and 2 shows higher catalytic activity compared to 1.