镧系元素硝酸盐与缩二脲固体配合物的合成及性质

我们在无水乙醇中,合成了除钜以外的十四种镧系元素硝酸盐与缩二脲的固体配合物。并用元素分析、DTA—TG、X—射线粉末衍射、红外光谱以及电导等手段研究了这些配合物的组成和性质。基于元素分析结果,红外光谱中M—O键、配位NO_3~-及游离NO_3~-的伸缩振动的存在,以及摩尔电导值,可建议它们的化学式分别为: [LnB_3(NO_3)_2]·NO_3 (Ln=La—Sm,B—缩二脲) [LnB_4(NO_3)_2)·NO_3 (Ln=Eu—Lu)     

Tetrakis(triphenylphosphine oxide) complexes of the lanthanide nitrates; synthesis, characterisation and crystal structures of [La(Ph3PO)4(NO3)3]·Me2CO and [Lu(Ph3PO)4(NO3)2]NO3

The reaction of Ln(NO₃)₃·6H₂O (Ln=La, Ce, Pr or Nd) with a sixfold excess of Ph₃PO in acetone formed [Ln(Ph₃PO)₄(NO₃)₃]·Me₂CO. The crystal structure of the La complex shows a nine-coordinate metal centre with four phosphine oxides, two bidentate and one monodentate nitrate groups, and PXRD studies show the same structure is present in the other three complexes. In CH₂Cl₂ or Me₂CO solutions, ³¹P NMR studies show that the complexes are essentially completely decomposed into [Ln(Ph₃PO)₃(NO₃)₃] and Ph₃PO. Similar reactions in ethanol gave [Ln(Ph₃PO)₃(NO₃)₃] only. In contrast for Ln=Sm, Eu or Gd, only the [Ln(Ph₃PO)₃(NO₃)₃] are formed from either acetone or ethanol solutions. For the later lanthanides Ln=Tb–Lu, acetone solutions of Ln(NO₃)₃·6H₂O and Ph₃PO gave [Ln(Ph₃PO)₃(NO₃)₃] only, even with a large excess of Ph₃PO, but from cold ethanol [Ln(Ph₃PO)₄(NO₃)₂]NO₃ (Ln=Tb, Ho–Lu) were obtained. The structure of [Lu(Ph₃PO)₄(NO₃)₂]NO₃ shows an eight-coordinate metal centre with four phosphine oxides and two bidentate nitrate groups. In solution in CH₂Cl₂ or Me₂CO the tetrakis-complexes show varying amounts of decomposition into mixtures of [Ln(Ph₃PO)₃(NO₃)₃], [Ln(Ph₃PO)₄(NO₃)₂]NO₃ and Ph₃PO as judged by ³¹P{¹H} NMR spectroscopy. The [Ln(Ph₃PO)₃(NO₃)₃] also partially decompose in solution for Ln=Dy–Lu, forming some tetrakis(phosphine oxide) species.     

3—磺基—4—羟基香豆素希土化合物的合成及性质

在不同条件下制得三种类型的希土与3-磺基-4-羟基香豆素(H₂SHC)化合物,元素分析确定了它们的组成分别为Ln(HSHC)₃·9H₂(Ln=La,Pr,Nd,Gd,Dy,Er,Yb,Y),Ln₂(SHC)₃.nH₂O(Ln:La,Pr,Nd,Sm,Gd,N:4或6)和Na₃Ln(SHC)₃·H₂O(Ln=Er,Yb).并通过它们的摩尔电导戌\重,溶解度,红外光谱和电子吸收光谱对各种化合物进行了结构和性质的研究。     

One-step synthesis of pentavalent triphenylantimony derivatives Ph3Sb(OSiR3)2, Ph3Sb(OCH2CH2)2NH and Ph3Sb(OCH2CH2NMe2)2: X-ray molecular structure of Ph3Sb(OSiMe3)2

Pentavalent bis(triorganosiloxy)triphenylantimony derivatives, Ph₃Sb(OSiR₃)₂ (R = Me, Ph), were synthesized by reaction of triphenylantimony with trimethyl- or triphenylsilanol in the presence of tert-butylhydroperoxide by the mild reaction conditions (0-5 °C, 2 h). The reaction of triphenylantimony with diethanolamine in the presence of tert-butylhydroperoxide gave the cyclic compound Ph₃Sb(OCH₂CH₂)₂NH. The mixture of Ph₃SbO and Ph₃Sb(OCH₂CH₂NMe₂)₂ was obtained by the reaction of triphenylantimony with 2-(N,N-dimethylamino)ethanol in the presence of tert-butylhydroperoxide.     

3—磺基—4—羟基香豆素希土化合物的合成及性质

在不同条件下制得三种类型的希土与3-磺基-4-羟基香豆素(H_2SHC)化合物,元素分析确定了它们的组成分别为Ln(HSHC)_3·9H_2(Ln=La,Pr,Nd,Gd,Dy,Er,Yb,Y),Ln_2(SHC)_3.nH_2O(Ln:La,Pr,Nd,Sm,Gd,N:4或6)和Na,Ln(3HC),·H:O(Ln:Er,Yb).并通过它们的摩尔电导戌\重,溶解度,红外光谱和电子吸收光谱对各种化合物进行了结构和性质的研究。     

Syntheses of gold-manganese and gold-rhenium clusters, [(Ph3PAu)3M(CO)4] and [(Ph3PAu)4M(CO)4] (M = Mn, Re), and the crystal structure of [(Ph3PAu)4Mn(CO)4]BF4

The specific additions of one, three or four Ph₃PAu groups to [M(CO)₅]⁻ (M=Mn, Re) are described. Thus [M(CO)₅] ⁻ in THF reacts with [(Ph₃PAu)₃O]BF₄ to give [(Ph₃PAu)₄Mn(CO)₄]BF₄. An X-ray crystal structure of the M = Mn example shows the cation to have a trigonal bipyramidal Au₄Mn core with the Mn in an equatorial site. The previously known neutral (Ph₃PAu)₃M(CO)₄ clusters are formed by addition of two Ph₃PAu groups, using the mixed reagent [(Ph₃PAu) ₃O]BF₄/[ppn][Co(CO)₄], to Ph₃PAuM(CO)₅, which itself is readily prepared from [M(CO)₅]⁻ and Ph₃PAuCl.     

Preparation and characterization of single crystals[Ln(TBPO)4(NO3)2]NTf2 (Ln=Eu,Gd)

Two single crystals[Ln(TBPO)₄(NO₃)₂]NTf₂ (Ln=Eu, Gd) were prepared and characterized by element analysis, single crystal X-ray diffraction, PXRD, FT-IR, TGA and fluorescence spectroscopy. The two compounds have similar coordinate structures, in which the central metal ion is coordinated by four TBPO (Tri-n-butylphosphine oxide) molecules and two bidentate nitrates, while NTf₂^-(bis(trifluor-(bis(trifluoromethylsulfonyl) imide anion) acts as the counter anion. The packing modes of the two crystals are same. The two single crystals are the focus on 8-coordinate tetra-TRPO complexes (TRPO is Trialkyphosphine oxides).     

稀土硝酸盐与穴醚(2.2)及穴醚(2.2.2)配合物的合成和性质

由三价稀土、镧、铕和镱的硝酸盐分别与穴醚(2.2),穴醚(2.2.2)反应,合成相应的五种固体配合物,并进行了元素分析,IR,NMR,TG,DTA,电化学等性质的研究。     

Schiff碱型大环配合物的合成及性质研究

本文合成了一个新的Schiff碱型大环配体“三氧二(?)”(L),及其C(?)(Ⅱ)、Ce(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)、Cd(Ⅱ)、Ag(Ⅰ)的配合物,经红外光谱、电导、元素分析等推算了它们的组成并指认了谱带的归属.对Cu(Ⅱ)配合物进行了电子顺磁共振谱、光电子能谱分析.     

四种新型单取代氨基酸四苯基卟啉锌配合物的合成和光谱表征

本文合成了四种新的单取代氨基酸四苯基卟啉锌配合物Zn［Val-TPP］、Zn［Glu-TPP］、Zn［Tyr-TPP］和Zn［Trp-TPP］。通过化学分析和元素分析确定了配合物的组成，研究了它们的紫外、红外、荧光和激光拉曼光谱。     

Structure, 31P and 13C chemical shift anisotrophy of (CH3)3P, (CH3)3PO, (CH3)3PS and (CH3)3PSe as determined by liquid crystal NMR spectroscopy

The ¹³P and ¹³C spectra of the triply ¹³C labelled molecules (CH₃)₃P, (CH₃)₃PO, (CH₃)₃PS and (CH₃)₃PSe oriented in a nematic phase are reported. The CPC bond angles have been measured. The ¹³P chemical shift tensor shows a large anisotropy except in the case of (CH₃)₃P. The abnormal large value observed for the PSe bond length suggests a large anisotropy of the ¹J(PSe) spin coupling.     

Synthesis and structural behavior of the P-functional organotin chlorides [Ph2P(CH2)3]2SnCl2, Ph2P(CH2)3SnCl2Me, and Ph2P(CH2)nSnCl3 (n=2, 3)

The P-functional organotin dichloride [Ph₂P(CH₂)₃]₂SnCl₂ (3) is synthesized by reaction of Ph₂P(CH₂)₃MgCl with SnCl₄ independently of the molar ratio of the starting compounds. The corresponding organotin trichlorides Ph₂P(CH₂)_nSnCl₂R (4: n=2, R=Cl; 5: n=3, R=Cl; 6: n=3, R=Me) are formed in a cleavage reaction of Ph₂P(CH₂)_nSnCy₃ (n=2, 3) with SnCl₄ or MeSnCl₃, respectively. The main features of the crystal structures of 3–6 are both intra- and intermolecular PSn coordinations and the existence of intermolecular Sn---ClSn bridges. For further characterization of the title compounds, the adducts 4(Ph₃PO)₂ (7) and 5(Ph₃PO) (8), as well as the P-oxides and P-sulfides of 3–6 (9–15), are synthesized. The results of crystal structure analyses of 7, 11, 12, and 14 are reported. The structures of 9–15 are characterized by intramolecular P=XSn interactions (X=O, S). A first insight into the structural behavior of the compounds 3–15 in solution is discussed on the basis of multinuclear NMR data.     

Crystal structure of [Pd(P(i-Pr)3)2(acac)]BF4

A single crystal X-ray diffraction study is carried out for [Pd(P(i-Pr)₃)₂(acac)]BF₄, T = 150(2) K. Crystal data: a = 10.2935(4) ?, b = 11.3591(5) ?, c = 13.8728(6) ?, α = 89.154(2)°, β = 68.448(1)°, γ = 85.032(1)°, P-1 space group, V = 1502.75(11) ?³, Z = 2, d _x = 1.354 g/cm³.     

镧系稀土四元配合物Ln(NO_3)_2(phen)_2(CH_3COCHCOCH_3)的合成及晶体结构表征

以乙酰丙酮(Hacac)、邻菲咯啉(phen)、硝酸根为配体,8-羟基喹啉为酸度调节剂合成出一个系列的镧系轻稀土四元配合物Ln(NO3)2(phen)2(CH3COCHCOCH3)(Ln=La,Ce,Pr,Nd,Sm)。配合物的结构与性质由元素分析,IR,1HNMR和TGA等表征。单晶Ce(NO3)2(phen)2(CH3COCHCOCH3)·H2O结构经由X射线衍射仪分析表明,晶体属单斜晶系,空间群P21/n,晶胞参数为a=1.11017(8)nm,b=0.98401(7)nm,c=1.34453(10)nm,β=102.0530(10)°,V=1.43641(18)nm3,Dc=1.715g·cm-3,Z=2,F(000)=742。配合物呈单核结构,中心离子Ce髥配位数为10。     

COPOLYMERIZATION OF BUTADIENE AND ISOPRENE CATALYZED BY V(acac)_3-Al(i-Bu)_2Cl-Al_2Et_3Cl_3 CATALYST AND CHARACTERIZATION OF THE PRODUCTS

Copolymerization of butadiene and isoprene catalyzed by the catalyst system V(acac)_3-Al(i-Bu)_2Cl-Al_2Et_3Cl_3 has been studied. Composition, microstructure, crystallinity and melting point of the copolymer obtained were determined by PGC, IR, X-ray diffraction and DSC methods respectively. The results revealed that the product was a copolymer and not a blend. The butadiene units presented in the copolymer were of trans-1,4-configuration, while the isoprene units were of both trans-1,4-and 3,4-forms. The melting point and crystallinity of the copolymer decrcascd with increase of molar ratio of isoprene to hutadiene.     

环氧化合物以三异丁基铝-水-双(2,4-戊二酮基)锌水合物为催化剂的共聚

本文以i-Bu_3Al-H_2O-Zn(acac)_2为催化剂,对环氧氯丙烷、环氧乙烷和环氧丙烷的三元共聚进行了研究。结果表明,这种三元共聚橡胶具有良好的性能,其耐寒性可与丁腈-18相媲美,耐油性比丁腈-18为佳,而耐臭氧老化性是丁腈橡胶所不能比拟的。     

CRYSTAL STRUCTURE OF A HETERONUCLEAR LANTHANIDE COMPLEX OF ERBIUM-YTTRIUM AND GLYCINE[ErY(GlY)_6(H_2O)_4](ClO_4)_65H_2O

The title complex [ErY(Gly)_6(H_2O)_4](ClO_4)_6 5H_2O has been synthesized.Its crystalstructure has been determined by X-ray diffraction method.The crystal is triclinic with space groupP1.The unit cell parameters are as follows:a=11.518(4),b=14.105(7),c=15.530(6) ,α=96.61(3),β=102.74(3),γ=105.70(3)°,V=2327.7(17) ~3,Z=2,Dc=2.091g/cm~3.The structure has been refinedto a final R of 0.0785.The crystal is an infinite chain complex,in which four carboxyl groups fromglycine molecules bridge the Er(Ⅲ)and Y(Ⅲ)ion,other two carboxyl groups bridge two adjacentEr(Ⅲ)or two Y(Ⅲ)ions.