四甲基双硅桥联环戊二烯基稀土金属有机配合物的合成及[Me4Si2(C5H4)2Sm(μ-Cl)(THF)]2的晶体结构研究

四甲基双硅桥联环戊二烯基钠与无水三氯化稀土在THF溶剂中反应合成了标题配合物Me₄Si₂(C₅H₄)₂LnCl[Ln:3Nd,4Sm,5Gd,6Y]和配合物Me₄Si₂(C₅H₄):Ln(C₅H₅)(THF)n[Ln:1La,n=1;2Pr,n=0].通过元素分析、¹HNMR、13CNMR和MS确证了配合物的结构,在THF溶液中重结晶获得配合物4的单晶,x射线衍射证明晶体结构为二聚体,4为单斜晶系,空间群为P2₁/c,晶体学数据a=1.2982(3)nm,b=1.2269(3)nm,c=1.3681(2)nm,β=96.79(2)°,V=2.162(1)nm³,Z=2,D_x=1.53g/cm³,偏差因子R=0.068.     

新型金属-双二硫杂戊烯(M-BDT)配合物的合成、表征及X射线的指标化

合成了4个新型NiBDT配位化合物,BDT为具有9个S原子的杂戊烯.元素分析、IR谱、UV谱确定这4个新配合物的化学式分别为[(CH₃)₄N]₂[Ni(C₅S₉)₂](1),[(C₂H₅)₄N]₂·[Ni(C₅S₉)₂](2),[(C₄H₉)₄N]₂[Ni(C₅S₉)₂](3),[(C₆H₅)(CH₃)₃N]₂[Ni(C₅S₉)₂](4).采用Ito法对配合物1的X射线粉末图进行了指标化,确定该晶体属单斜晶系,简单晶格,晶胞参数:a=0.680nm,b=0.714nm,c=2.302nm,γ=111.4°,Z=2.     

系列Ln(Ⅲ)配位聚合物(Ln=Eu,Sm,Tb,Pr,Gd)的合成及其荧光分析

采用水热法合成了4个具有1D结构的Ln(Ⅲ)配位聚合物,[Eu₂(C₉H₇O₂)₆(C₉H₇O₂H)(C₂H₅OH)]n(1)、[Sm(C₉H₇O₂)₃]n(2)、[Tb(C₉H₇O₂)₃]n(3)和[Gd(C₉H₇O₂)₃]n(4)(C₉H₈O₂=肉桂酸)。 通过X射线单晶衍射确定了它们的结构。 这4个Ln(Ⅲ)配合物中,Ln(Ⅲ)的配位数均为9,桥配体均为肉桂酸根,但其配位方式有差异。 对配合物进行了IR、UV-Vis-NIR和荧光光谱等表征。 分析了各配合物的荧光发射,结果表明,在可见区,配合物1发射较明显的红光,配合物2、3发射绿光,配合物4发射蓝光,但很弱。 讨论了具有刚柔相混杂性质的肉桂酸配体对配位聚合物的构筑及稀土离子发光的影响。     

两种苯磺酸铜配合物的结构及催化性能研究

硝酸铜分别与对氨基苯磺酸钠和苯磺酸钠反应,合成了对氨基苯磺酸铜[Cu(p-NH₂C₆H₄SO₃)₂(H₂O)₂]·2H₂O(配合物1)和苯磺酸铜[Cu(H₂O)₆](C₆H₅SO₃)₂(配合物2)。通过红外光谱(IR)、热重分析(TG)、单晶X-射线衍射(X-ray)、粉末X-射线衍射(PXRD)、扫描电镜(SEM)和比表面积分析(BET)技术对配合物的结构、组成及热稳定性进行了表征,确定了分子结构及表面形貌。并以Biginelli反应为探针,考察了配合物的催化性能,实验证明,配合物1和2均具有催化活性,且配合物2的催化效果优于配合物1(CCDC∶1∶2123933;2∶2124071)。     

二(四氢糠基茚)稀土氯化物的合成及晶体结构

将四氢糠基茚锂分别与无水三氯化钇和无水三氯化钆以摩尔比2;1反应,除去不溶物和溶剂后,将产物在甲苯/THF中冷冻得到晶体(C₄H₇OCH₂C₉H₆)₂LnCl[Ln=Y(1);Ln=Gd(2)].这两种配合物都是单分子无溶剂化合物,在空气中稳定.配合物1和2的晶体结构都属于正交晶系,P2₁2₁2₁空间群,晶胞参数分别为a=1.04252(9)nm,b=1.47455(12)nm,c=1.49799(13)nm,Z=4,Dc=1.508g/cm³;a=1.03701(10)nm,b=1.47233(12)nm,c=1.51354(14)nm,Z=4,Dc=1.699g/cm³.它们的结构相似,但空间构象不同.稀土中心离子分别与两个茚中的五元环和两个氧原子及氯原子成键,形成九配位结构.     

基于乙硫基取代的三层酞菁铕二聚体修饰ITO电极构筑电化学多巴胺和尿酸传感器

通过在水平和垂直两个方向上来扩展酞菁配合物的共轭结构, 合成了三明治三层酞菁铕二聚体配合物[Pc(SC₂H₅)₈]₂Eu₂[BiPc(SC₂H₅)₁₂]Eu₂[Pc(SC₂H₅)₈]₂, 使用Quasi-Langmuir-Sh?fer(QLS)方法将配合物薄膜修饰在氧化铟锡导电玻璃(ITO)电极表面, 利用多种谱学手段对配合物分子在薄膜内的排列进行表征, 发现分子采取J聚集模式Edge-on排列在ITO电极表面, 该薄膜具有良好的半导体性质, 导电率高达8.86×10^-5 S/cm. 将配合物薄膜修饰的ITO电极成功应用于多巴胺(DA)和尿酸(UA)的电化学灵敏检测, 最低检测限分别达到1.35和1.64 μmol/L, 灵敏度分别达到110和186.5 mA·μL·mol^-1 ·cm^-2.     

硅桥连双(三甲硅基环戊二烯基)钛化合物的合成及脱硅基反应

硅桥连双(三甲硅基环戊二烯基)双锂盐与TiCl₄·2THF反应,生成相应的钛化合物[E(C₅H₃SiMe₃)₂]TiCl₂[E=Me₂SiSiMe₂(3),Me₂SiOSiMe₂(5)],同时还分离到了脱一个三甲硅基的产物[E(C₅H₄)(C₅H₃SiMe₃)]TiCl₂[E=Me₂SiSiMe₂(4),Me₂SiOSiMe₂(6)].其中四甲基二硅氧桥连配体更容易发生这种脱硅基反应.通过元素分析、MS和¹HNMR谱表征了化合物3-6的分子结构.     

四甲基二硅桥联茚基环戊二烯基四羰基二铁的合成、结构及热重排反应

ClMe₂SiSiMe₂Cl顺序与茚基锂和环戊二烯基锂作用,生成(1-C₉H₇)Me₂SiSiMe₂C₅H₅.后者进一步与五羰基铁反应,得到硅硅桥联茚基环戊二烯基化合物[η⁵,η⁵-(1-C₉H₆)Me₂SiSiMe₂C₅H₄]Fe₂(CO)₄ (2).化合物2在加热条件下发生重排反应,给出硅硅键和铁铁键复分解产物([-)Me₂Si(η⁵-1-C₉H₆)Fe(CO)₂SiMe2(η⁵-C₅H₄)Fe(CO)₂(]-) (3).利用X射线衍射法,测定了2和3的分子结构.     

过氧氨三乙酸钛配合物分子前体热分解制备纯钛基复氧化物

在pH=2.5～4.0的条件下,以四氯化钛、过氧化氢和氨三乙酸为原料反应得到四种过氧酸钛配合物(NH₄)₄[Ti₂O～(O₂)2(ta)₂]·4H₂O (1), K₄[Ti₂O(O₂)₂(ta)₂]·6H₂O (2), Sr₂[Ti₂O(O₂)₂(ta)₂]·10H₂O (3)和Ba₂[Ti₂O(O₂)₂(ta)₂]·10H₂O (4) (H3ta=C₆H₆O₆N).配合物的EA, UV-vis, IR和X射线单晶分析表明它们含有相同的双核过氧氨三乙酸钛的阴离子结构,钛原子与过氧基团、四齿氨三乙酸和桥氧七配位.3和4中的阳离子锶和钡分别与周围的水分子和羧基氧形成九配位和十配位.配合物1, 3和4在空气中600℃分解,XRD分析表明分别得到金红石型TiO₂, SrTiO₃和四方BaTiO₃纯相.     

亚乙基桥联双茚锆、铪配合物的合成及催化丙烯选择性齐聚研究:茚环3-位取代基的影响

设计并合成了12个亚乙基桥联双茚类锆、铪配合物meso-/rac-1～7[ansa-C₂H₄-(3-R-4,7-Me₂-C₉H₃)₂MCl₂:M=Zr R=ⁿBu (meso-/rac-1),ⁱPr (meso-2),CH₂Cy (meso-/rac-3),Bn (meso-/rac-4),CH₂C₆H₄(4-CH₃)(meso-/rac-5);M=Hf,R=CH₂C₆H₄(4-CH₃)(meso-/rac-7);ansa-C₂H₄-{2-Me-3-Bn-5,6-[1,3-(CH₂)₃]C₉     

Synthese et etude des complexes [C5H4(CH2)3C5H4]Ti(C5H5)2 presentant un pont entre deux ligands cyclopentadienyles

The complex (di-η⁵-C₅H₄CH₂CH₂CH₂C₅H₄)Ti(η¹-C₅H₅)₂ (I) can be obtained unambiguously starting from the corresponding bridged titanocene dichloride. Attempts to synthesize the isomeric compounds (η⁵-C₅H₅)₂ Ti(di-η¹-C₅H₄-CH₂CH₂CH₂C₅H₄) (I′) by the action of a convenient bridged dianion on (C₅H₅)₂ TiCl₂ afford several compounds, one of them is the complex I. The possibility of interconversion of these complexes by a fluctional process is discussed.     

Dimethylchalkogenide als liganden in kationischen cyclopentadienyleisen-bis(phosphin)-komplexen: synthese, reaktivität und kristallstruktur von [C5H5Fe(P(OCH3)3)2(S(CH3)2)]PF6

Thermal displacement of coordinated nitriles RCN (R = CH₃, C₂H₅ or n-C₃H₇) in [C₅H₅Fe(L₂)(NCR)]X complexes (L₂ = P(OCH₃)₃)₂, (P(OC₆H₅)₃)₂ or (C₆H₅)₂PC₂H₄P(C₆H₅)₂ (DPPE)) by E(CH₃)₂ affords high yields of [C₅H₅Fe(L₂)(E(CH₃)₂)]X compounds (E = S, Se and Te; X = BF₄ or PF₆). Spectroscopic data and ligand displacement reactions are presented and discussed together with related observations on [C₅H₅Fe(CO)₂(E(CH₃)₂)]BF₄ compounds. The molecular structure of [C₅H₅Fe(P(OCH₃)₃)₂(S(CH₃)₂)]PF₆ was determined by a single-crystal X-ray diffraction study: monoclinic, space group P2₁/n-C⁵_2h (No. 14) with a = 8.4064(12), b = 11.183(2), c = 50.726(8) Å, β = 90.672(13)° and Z = 8 molecules per unit cell. The coordination sphere of the iron atom is pseudo-tetrahedral with an Fe---S bond distance of 2.238 Å.     

Synthesis and properties of alkyldicyclopentadienyl-vanadium(III) compounds

The compounds Cp₂VR (R = CH₃, C₂H₅, n-C₃H₇, n-C₄H₉, n-C₅H₁₁, CH₂C(CH₃)₃ or CH₂Si(CH₃)₃) have been prepared from Cp₂ VCl and RMgX in n-pentane. The air-sensitive compounds are stable at room temperature, but decompose between 65 and 138°C. The thermal stability decreases in the order R = CH₃ CH₂Si(CH₃)₃ > C₂H₅ > CH₂C(CH₃)₃ > n-C₅H₁₁ > n-C₄H₉ > n-C₃H₇. Compounds with R = i-C₃H₇ or t-C₄H₉ could not be obtained.     

Stabile Bis(η-alkin)MCl2-komplexe; Darstellung und reaktivität

The synthesis and reactivity of {(η⁵-C₅H₄SiMe₃)₂Ti(CCSiMe₃)₂} MCl₂ (M = Fe: 3a; M = Co: 3b; M = Ni: 3c) is described. The complexes 3 are accessible by the reaction of (η⁵-C₅H₄SiMe₃) ₂Ti(CSiMe₃)₂ (1) with equimolar amounts of MCl₂ (2) (M = Fe, Co, Ni). 3a reacts with the organic chelat ligands 2,2′-dipyridyl (dipy) (4a) or 1,10-phenanthroline (phen) (4b) in THF at 25°C to afford in quantitative yields (η⁵-C₅H₄SiMe₃)₂Ti(CSiMe₃)₂ (1) and [Fe(dipy)₂]Cl₂ (5a) or [Fe(phen)₂]Cl₂ (5b). 1/n[Cu^IHal]_n (6) or 1/n[Ag^IHal]_n (7) (Hal = Cl, Br) react with {(η⁵ -C₅H₄SiMe₃)₂Ti(CCSiMe₃)₂}FeCl₂ (3a), by replacement of the FeCl₂ building block in 3a, to yield the compounds {(η⁵-C₅H₄SiMe₃)₂Ti(C CSiMe₃)₂}Cu^IHal (8) or {(η⁵-C₅H₄SiMe₃)₂Ti(CSiMe₃)₂}Ag^IHal (9) (Hal = Cl, Br), respectively. In 8 and 9 each of the two Me₃SiCC-units is η²-coordinated to monomeric Cu^I Hal or Ag^IHal moieties. Compounds 8 and 9 can also be synthesized by the reaction of (η⁵-C₅H₄SiMe₃)₂ Ti(CSiMe₃)₂ (1) with 1/n[Cu^IHal]_n (6) or 1/n [Ag^IHal]_n (7) in excellent yields. All new compounds have been characterized by analytical and spectroscopic data (IR, ¹H-NMR, MS). The magnetic moments of compounds 3 were measured.     

La-NMR-spektroskopie an allyllanthan(III)-komplexen

¹³⁹La-NMR chemical shifts were measured for several anionic complexes of formulae Li(C₄H₈O₂)_3/2 [La(ν³-C₃H₅)₄], [Li(C₄H₈O₂)₂][Cp′_nLa(ν³-C₃]H₅)_4−n] (Cp′ = Cp(ν⁵-C₅H₅); n = 1, 2 and Cp′ = Cp * (ν⁵-C₅Me₅); N = 1) and Li[R_nLa(ν³-C₃H₄)₄−n] (R = N(SiMe₃)₂; n = 1, 2 and R = CCsIMe₃; n = 4), as well as for neutral compounds for formulae La(ν³-C₃H₅)₃L_n (L = (C₄H₈O₂)_1.5, (HMPT)₂, TMED), Cp′_nLa(ν³-C₃H₅)_3−n (Cp′= Cp(ν⁵-Cp₅H₅), Cp *(ν⁵-C₅Me₅); n = 1, 2) and La(ν³-C₃H₂)₂X(THF)₂ X = Cl, Br, I). Typical ranges of the ¹³⁹La-NMR chemical shifts were found for the different types of complex independent of number and kind of organyl groups directly bonded to lanthanum.

Zusammenfassung

¹³⁹La-NMR-Spektroskopie wurde an einer Reihe anionischer Allyllanthanat(III)-Komplexe der Zusammensetzung ]- [La)ν³-C₃H₅)₄, [Li(C₄H₈)₂][Cp′_nLa(ν³-C₃H₅)_4−n(Cp′ = Cp(ν⁵-C₅H₅); n = 1, 2 und Cp′ = Cp * (ν⁵-C₅Me₅); N = 1) und Li[R_nLa(ν³-C₃H₅)_4−n (R = B(SiMe₃)₂; n = 1, 2 und R = CCSiMe₃; n = 4 sowie neutraler Allyllanthan(III)-Komplexe der Zusammensetzung La(ν³-C₃H₅)₃L_n (L_n = (C₄H₈O₂)_1.5, (HMPT)₂, TMED), Cp′_n, La(ν³-C₃H₅)_3−n (Cp′ = Cp(ν⁵-C₅H₅), Cp * (ν⁵- Cp₅Me₅); n = 1, 2) und La(ν³-Cp₃H₅)₂X(THF)₂ (X = Cl, Br, I) durchgefürt. In Abhängikeit von der Anzahl und der Art der am Lanthan gebundenen Gruppen wurden für die verschieden Komplextypen charakteristische Resonanzbereiche ermittelt.     

Degradation Method for Preparing Organo-Arsenic and-Antimony Polytungstates and Comparative Study of Corresponding Polymolybdates

In repeating and extending the syntheses of organo-arsenic polytungstates,we found that the "Degradation Method",taking sodium metatungstate as the starting material,was much more profita-ble.The known compound (CN3H6)5[(C6H5As)2W6O25H]2H2O(1) was read-ily reproduced with a high yield.A new compound (CN3H6)6[(p-OH,m-NO2C6H3As)2W6O25](2) was likewise synthesized.This "Degradation Method" using the reaction of sodium metatungstate with organo-anti-monate led to the isolation of four compounds with definite composition although amorphous in appearance.The preparations of organo-arsenic polymolybdates and organo-antimony polymolybdates were also studied and six new organo-arsenic polymolybdates were isolated: (CN3H6)5[(C6H5As)2MoO25H]H2O(3),(CN3H6)4[(n-C3H7As)2Mo5O21]2H O (4),(CNH)4[(n-C3H7As)2Mo6O24](5),Cs2[(CH3)2AsMo4O15H](6),相似文献   

Zur oxidativen spaltung von metall—metall-bindungen in metallorganischen verbindungen mittels ferriceniumkationen

The dinuclear organometallic compounds ((C₅H₅Fe(CO)₂)₂, CO₂(CO)₈ and (C₅H₅NiCO)₂) are oxidized by [(C₅H₅)₂Fe]X (X = BF₄, PF₆) in the presence of neutral ligands L to form the cationic organometallic complexes [C₅H₅Fe(CO)₂L]X, [trans-Co(CO)₃L₂]X and [C₅H₅NiL₂]X in high yield.     

Cooperative effects in binuclear zirconocenes: Their synthesis and use as catalyst in propene polymerization

The mono- and bis-cyclopentadienyl compounds 1-(Cp″)-4-(CH₃)C₆H₄ (1) and 1, 4-(Cp″)₂C₆H₄ (2) (Cp″ = 3,4-dimethylcyclopenta-1,3-diene-1-yl) have been synthesized. The reactions of the lithium salts of 1 and 2 with CpZrCl₃ · dme (dme = dimethoxyethane) and Cp*ZrCl₃(CP* = C₅(CH₃)₅) yielded the mono- and bi-nuclear bridged zirconocenes 1-(Cp″ZrCpCl₂)-4-(CH₃)C₆H₄ (3), 1,4-(Cp″ZrCpCl₂)₂C₆H₄ (4) and 1,4-(Cp″ZrCp*Cl₂)₂C₆H₄ (5). When activated with methylaluminoxane (MAO), the mono- and bi-nuclear zirconocenes 3 and 4 catalyse the polymerization of propene. The influence of the catalyst composition on the polymerization kinetics and molecular weight is discussed.     

Stability of the silicon-ruthenium bond in the presence of a strong nucleophile. Phase sensitive H NMR COSY and crystal structure of Ru(CO)2(NH2CH2C6H5)2(Si(C6H5)(CH3)2)I

The ruthenium(II) complex Ru(CO)₂(NH₂(NH₂CH₂C₆H₅)₂(Si(C₆H₅)(CH₃)₂)I has been prepared by the reaction of Ru(CO)₄(Si(C₆H₅)(CH₃)₂)I with benzylamine. Two-dimensional homonuclear ¹H NMR experiments examine the scalar coupling of the enantiotopic amino and methylene protons of the benzylamine ligand. X-ray analysis of Ru(CO)₂(NH₂CH₂C₆H₅)₂(Si(C₆H₅)(CH₃)₂)I·1/3C₅H₁₂ (triclinic; P ; a = 14.266(4), b = 15.748(5), c = 20.082(6) Å; = 94.38(3), β = 96.30(2), γ = 101.52(2)°) indicates three crystallographically unique complexes form a clathrate with a pentane guest.