铂氢化物trans-[PtH(tu)(PPh_3)_2]Cl(tu)(THF)_2(tu=SC(NH_2)_2)的结构

制得含硫脲配体的铂氢化物单晶trans-[PtH(tu)(PPh_3)_2]Cl(tu)(THF)_2,其结构测定结果为:C_(46)H_(55)N_4O_2P_2S_2ClPt M=1052.6,单斜晶系,空间群为 P2_1/c,a=12.103(1),b=21.619(3),c=20.189(4)(?),β=103.31(0)°,V=5140(2)(?)~3,Z=4,D_c=1.360g·cm~(-3),F(000)=2128,R=0.050,R_w=0.063.Pt(Ⅱ)与两个磷、一个硫脲分子的硫和一个氢相配合,形成四边形配位。     

DECARBONYLATION OF ACYLCHLOROBIS-(TRIPHENYLPHOSPHINE) PLATINUM(II) COMPLEXES PROMOTED BY TIN(II) CHLORIDE

Abstract

While it might be expected that the availability of vacant coordination sites in the four coordinate acyl complexes trans[Pt(PPh₃)₂ (RCO)Cl] provides low energy pathways for alkyl and aryl migration and subsequent decarbonylation, the decarbonylation has been previously achieved only at elevated temperatures. The addition of SnCl₂ greatly facilitates decarbonylation of [Pt(PPh₃)₂ (RCO)Cl] where R is CH₃, C₂ H₅, Y[sbnd]C₆ H₄. Compounds of the type [Pt(PPh₃)₂ (RCO)SnCl₃] and [Pt(PPh₃)₂ R(SnCl₃)] have been isolated. The removal of SnCl₂ from these compounds has been achieved with ethanol. A kinetic study of the decarbonylation of [Pt(PPh₃)₂ (RCO)SnCl₃] (where R is CH₃, C₂ H₅, Y[sbnd]C₆ H₄ for Y=H, CH₃, CH₃ O, NO₂, Cl) is reported. The role of 3 and 5 coordinate intermediates in alkyl-aryl migrations in Pt(II) systems is discussed.     

STUDIES ON BINUCLEAR COMPLEXES.CRYSTAL AND MOLECULAR STRUCTURE OF [Pd(μ-Ph_2Ppy)Cl]_2·0.3CH_2Cl_2

<正> [Pd(u-Ph2Ppy)Cl]2.0. 3CH2C12, Mr = 835. 70, monoclinic, space group C2/c with a=30. 405(4), b= 17. 868(2),c=12. 955(2) A,B=98. 40(1) ,V = 6962. 6A3;Z=8,Dx=1. 59 g/cm3,final R=0. 044 and Rw= 0. 058 for 3190 observed independent reflections. The distance between the two palladium atoms is 2. 5885(4) A. Each Pd ( I ) atom has a square-planar stereochemistry . There is a pronounced twist ad-out the Pd-Pd bond with the result that the dihedral angle between the coordination planes of two Pd atoms is 37. 6.     

2,6—二乙酰吡啶类双希夫碱配合物的合成和研究 Ⅱ.Cu(Ⅱ)配合物的合成和研究

合成了五个2,6-二乙酰吡啶缩肼基硫代甲酸酯双希夫碱合铜(Ⅱ)配合物,用元素分析、磁化率、红外光谱及紫外-可见光谱等对它们进行了表征,研究了配合物的电化学性质和Cu_3L_2~2X_2(X=Cl~-、SCN~-)的光电子能谱。结果表明:五个Cu(Ⅱ)配合物均为三核配合物,在Cu_3L_2~2(SCN)_2中存在Cu(Ⅱ)间的自旋—交换作用。     

1-羟基-2-乙酰基呫吨酮类希夫碱双核配合物的研究 Ⅰ Cu(Ⅱ)配合物的合成和表征

以1-羟基-2-乙酰基咕吨酮和肼基二硫代甲酸甲酯缩合所得希夫碱(以H_2L表示),与Cu(Ⅱ)反应制得三种双核配合物。通过元素分析、红外、紫外-可见,磁化率、电子顺磁共振和循环伏安法等对配合物进行了表征和研究.表明这些配合物中,在所处化学环境不同的两个Cu(Ⅱ)之间存在较弱的自旋交换作用。桥联配体为醋酸根时,表现出不可逆的氧化还原性质,其余配合物显示准可逆的双电子转移过程.在吡啶存在时,醋酸根配位的双核铜配合物的氧化还原可逆性增加,其余配合物表现出可逆的两步单电子转移过程,同时还原电位正向移动.     

2,6-二乙酰吡啶类双希夫碱配合物的合成和研究 Ⅱ.Cu(Ⅱ)配合物的合成和研究

合成了五个2,6-二乙酰吡啶缩肼基硫代甲酸酯双希夫碱合铜(Ⅱ)配合物,用元素分析、磁化率、红外光谱及紫外-可见光谱等对它们进行了表征,研究了配合物的电化学性质和Cu₃L₂²X₂(X=Cl^-、SCN^-)的光电子能谱。结果表明:五个Cu(Ⅱ)配合物均为三核配合物,在Cu₃L₂²(SCN)₂中存在Cu(Ⅱ)间的自旋-交换作用。     

NMR and kinetic studies of the interactions of [Au(cis-DACH)Cl2]Cl and [Au(cis-DACH)2]Cl3 with potassium cyanide in aqueous solution

The interactions of [Au(cis-DACH)Cl₂]Cl and [Au(cis-DACH)₂]Cl₃ [where cis-DACH is cis-1,2-diaminocyclohexane] with enriched KCN were carried out in CD₃OD and D₂O, respectively. The reaction pathways of these complexes were studied by ¹H, ¹³C, ¹⁵N NMR, UV spectrophotometry, and electrochemistry. The kinetic data for the reaction of cyanide with [Au(cis-DACH)₂]Cl₃ are k = 18 M^?1s^?1, ?H^≠ = 11 kJ M^?1, ?S^≠ = ?185 JK^?1 M^?1, and E_a = 13 kJ M^?1 with square wave voltammetric (SWV) peak +1.35 V, whereas the kinetic data for the reaction of cyanide ion with [Au(cis-DACH)Cl₂]Cl are k = 148 M^?1s^?1, ?H^≠ = 39 kJM^?1, ?S^≠ = ?80 JK^-1 M^?1, and E_a = 42 kJM^?1 along with SWV peak +0.82 V, indicating much higher reactivity of [Au(cis-DACH)Cl₂]Cl toward cyanide than [Au(cis-DACH)₂]Cl₃. The interaction of these complexes with potassium cyanide resulted in an unstable [Au(¹³CN)₄]^? species which readily underwent reductive elimination reaction to generate [Au(¹³CN)₂]^? and cyanogen.     

Me_4Bzo_2[14]六烯(2-)N_4金属配合物的结构和反应性研究 Ⅰ.溴碘加成物的合成和振动光谱研究

本文合成了Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)、Cu(Ⅱ)大环配合物及其溴碘加成物,研究了远红外和Raman光谱,对MN_4局部进行了伸缩振动的简正坐标分析,求得了各化合物的键角和伸缩力常。通过Raman光谱初步确定了溴碘的存在形式。对溴碘加成物的叠层结构和各化合物的成键进行了讨论。     

Crystal structures of bis(diethylenetriamine)cobalt(III) Heptachlorodimercurate(II)mer-[Co(Dien)2]Hg2Cl7 and (diethylenetriamine)glycylglycinato(1-) cobalt(III) hexachlorodimercurate(II) [Co(Dien)HGlygly]Hg2Cl6

An X-ray diffraction analysis was performed for crystalline [Co(Dien)₂]Hg₂Cl₇ (a = 14.452(2), b = 9.831(1), c = 15.967(2) åΒ = 97.17(1)?, space group P2₁/c, Z = 4) and [Co(Dien)HGlygly]Hg₂Cl₆ (a = 7.693(1), b = 14.439(2), c = 19.961(2) å, Β = 100.31(1)?, space group P2₁ Z = 2), where Dien is diethylenetriamine and HGlygly is the glycylglycine anion [H₂NCH₂C(OH) = NCH₂CO₂]. The anionic moiety is represented by isolated centrosymmetric ions [Hg₄Cl₁₄]_6- in the former and by infinite chains [Hg₂Cl₆] _n ^2n- in the latter (the chain is composed of two alternating vertex-sharing nonequivalent tetrahedral groups HgCl₄. In the cobalt(III) complex cations, the extreme donating atoms of the Dien and HGlygly ligands are in the trans positions of the coordination octahedron.     

邻香兰素与二胺类双希夫碱镧配合物的合成

某些稀土希夫碱配合物可用于制备核磁共振位移试剂、稀土发光塑料等特殊应用,因而受到人们的重视。估计也会在稀土发光材料方面获得应用。有关邻香兰素(2-羟基-3-甲氧基苯甲醛)与乙二胺(或邻苯二胺、间苯二胺)缩合而成的双希夫碱和镧形成的配合物研究尚未见文献报导。我们在非水体系中用硝酸镧(Ⅲ)和这些双希夫碱反应,合成出固体配合物,研究了它们的组成、结构及某些物理化学性质。     

CRYSTAL AND MOLECULAR STRUCTURE OF BIS(2-ME-THOXYETHYL-CYCLOPENTADIENYL) ERBIUM CHLORIDE

<正> Complex Cp'2 ErCl(Cp'=2-methoxyethylcyelopentadienyl)(I)has been synthesized by the reaction of Cp' Na and ErCl3 in THF It crystallizes in space group Pnma with a=12.269(0),b=11.742(6),c=11.197(2)A,V=1613.1A3,Dc=1.849 g/cm3,Z=4,A=0.71073 A,μ(MoKa)=54.38 cm-1,F(000)=876,R=0.043,Rw=0.046.The Er atom is formally nine-coordinated with a pseudo-trigonal bipyramidal geometry with the "equatorial" plane composed of the Er atom,the Cl atom and the centers(1)and(2)of the two Cp rings(Cp=cy-clopentadienyl).The molecule is located at the crystallographic mirror plane through the atom C(3),C(4),C(S),Er,O(1)and C(6).The atom Cl and the atoms of Cp'(2)(except C(16)and C(16'))are disordered with an occupancy of 0.5 each.     

SYNTHESIS OF FUSED AND SPIRO HETEROCYCLIC COMPOUNDS DERIVED FROM 3,5-PYRAZOLIDINEDIONE DERIVATIVES

Abstract

The reaction of compound 1 with triethyl orthoformate afforded 2, which in turn reacted with CS₂ and active methlyene compounds or malononitrile to give dithiolane and 4-malononitrile methylene derivatives 3,4, respectively. Treatment of compound 4 with active methylene compounds afforded spiro cyclopentene derivatives 5_a-c. Compound 1 was reacted with bromomalononitrile or CS₂ and halocompounds to afford furo-. thieno- and dithiolano-pyrazole derivatives 6–11, respectively. The reaction of compound 12 with phenacyl bromide or benzylidenemalononitrile furnished oxathiol-2-ylidene and pyridinethione derivatives 13,14, respectively. The dibromo derivative 16 was reacted with CS₂ and active methylenes or malononitrile to obtain spiro dithietanes 17a-e and 4-dicyano-methlyene derivative 22, respectively. Compounds 17 underwent a cycloaddition reaction with thioglycolic acid, N-phenylbenzohydrazindoyl bromide, 2,5-dimethylfuran and 1-phenyl-3,5-pyrazolidinedi one to give cycloadducts 18–21, respectively. Treatment of > o-aminothiophenol or o-phenylenediamine with the dicyano compound 22 leads to the formation of spiro thiazepine or spiro diazine derivatives 23_a,b . The arylidene derivatives 24 was reacted with S,S-acetals, N,S-acetals or ammonium dithiocarbamate to afford dithiane, oxazine or pyrazolodithiocarbamate derivatives 25–29, respectively. Chemoselective cyclization of compound 29 with H₂SO₄, NaOH or MeI gave compounds 30–32, respectively. Benzopyrano derivatives 34,36 were obtained through the reaction of compound 1 with a mixture of thiourea, triethyl orthoformate and ethyl cyanoacetate or with cyanoketene S,S diacetals, respectively.     

Synthesis, characterization and anti proliferative effect of [Au(en)2]Cl3 and [Au(N-propyl-en)2]Cl3 on human cancer cell lines

Two Au(III) complexes of the type [Au(en)2]Cl3 (2a) and [Au(N-pr-en)2]Cl3 (3a) were synthesized by reacting Auric acid (HAuCl(4)·3H2O) with 2 equiv. ethylenediamine (en) or N-alkyl substituted ethylenediamine ligands. This metallodrug was characterized by various analytical and spectroscopic techniques such as elemental analysis, UV-Vis, Far-IR, 1H NMR and solution 13C as well as solid 13C and 15N NMR. Potentiality of [Au(en)2]Cl3 and [Au(N-pr-en)2]Cl3 as an anti-cancer agent were investigated by measuring some relevant physicochemical and biochemical properties such as stability of Au-N bonds by vibrational stretching from Far IR as well as cytotoxicity and stomach cancer cell inhibiting effect, respectively. The solid-state 15N NMR chemical shift shows that the ligand is strongly bound to gold(III) centre via N atoms. The computational study of 2a shows that the gold coordination sphere adopts distorted square planar geometry with bidentate ethylenediamine ligands acting as a tetradentate chelate. While stable in the solution state, the in vitro biological studies performed with these compounds 2a in solution showed higher activity towards the inhibitory effects of the human cancer cell lines such as prostate cancer (PC-3) and gastric carcinoma (SGC-7901) than that of the N-substituted gold(III) complex (3a). Cytotoxicity of the new compounds has also been estimated in PC-3 and SGC-7901 cells.     

［Eu2(BA)6(bipy)2］的晶体结构和荧光光谱

标题配合物晶体属单斜晶系，P2₁/n空间群，晶胞参数a=1.4162(3) nm，b=1.5377(5) (nm), c=2.6017(5) nm, β=103.56(3°)， Z=4。标题配合物是双核分子，4个苯甲酸的羧基桥联两个中心Eu(Ⅲ)离子。它们又分别与1个苯甲酸的羧基的两个氧原子和一个联吡啶分子的两个氮原子螯合配位，形成4，4′-双帽三角棱柱体。两个Eu(Ⅲ)离子的Eu-O和Eu-N平均键长不等。两个Eu(Ⅲ)离子的化学环境略有不同。在配合物的 ⁷F₀→ ⁵D₀激发光谱里，580.17和580.31 nm处呈现两个锐峰，可以认为配合物具有两种Eu(Ⅲ)格位，选择激发配合物的 ⁵D₀能级，得到的 ⁵D₀→ ⁷F_1,2发光光谱表明配合物中Eu(Ⅲ)离子有不同的化学环境，这与晶体结构分析结果一致。     

金和铂的某些冠醚类配合物的合成与性质

制得5种金和铂的冠醚类配合物,用元素分析、红外和紫外光谱、摩尔电导和~1H核磁共振谱等方法研究了配合物的组成及其有关性质。     

THE AROMATICITY OF TRANSITION METAL COMPLEXES DERIVED FROM 1,2- AND 1,3-DITHIO-DIKETONES

Abstract

Fully conjugated cyclic transition metal complexes are potential aromatic species, showing complete cyclic delocalization of the p- and d-electrons. It was proposed earlier that such aromaticity could only be found in complexes with “even-numbered” ligands (type I), while complexes containing “odd” ligands (type II) should not show full delocalization and hence be classified as non-aromatic.     

PLATINUM(II) COMPLEXES OF P(III) CYCLOPHOSPHAMIDE DERIVATIVES

Abstract

The syntheses of the P(III) analogues of cyclophosphamide, isophosphamide and triphosphamide are reported. These compounds (4–6, respectively) polymerize easily at room temperature but are sufficiently stable in solution to react with Cl₂Pt(NCPh)₂, forming cis-Cl₂Pt(4)₂, cis-Cl₂Pt(5)₂ and cis-Cl₂Pt(6)₂ (complexes 9–11, respectively). Complex 10 can also be made by condensing cis-Cl₂Pt[ClPN(CH₂CH₂Cl)CH₂CH₂CHO]₂ with ClCH₂CH₂NH₂, while an alternate route to 9 and 11 is afforded by the condensation of cis-Cl₂Pt[Cl₂PN(CH₂CH₂Cl)₂]₂ with H₂NCH₂CH₂CH₂OH and ClCH₂CH₂NHCH₂CH₂CH₂OH, respectively. Complexes 9–11 exist in two diastereomeric configurations and these can be separated in the cases of 9 and 11 by column chromatography. ³¹P NMR spectral data for the complexes are discussed and the results of NCl antitumor screening are presented.     

β-二酮缩β-丙氨酸希夫碱的锰(Ⅲ)配合物

合成了锰(Ⅲ)的双核配合物Mn_2(Hacala-β)_2(O_2CMe)_4和三核配合物Mn_3O(bzala-β)_2(O_2CMe)_3·4H_2O,其中Hacala-β~-和bzala-β~(2-)分别是乙酰丙酮缩β-丙氨酸和苯甲酰丙酮缩β-丙氨酸希夫碱负离子。用电导率、磁化率、热分析、红外及紫外可见光谱等对它们的结构和性质进行了研究。     

聚乙烯醇衍生的聚离子复合物的研究——Ⅳ.聚离子复合物膜的力学行为及透过性能

The mechanical behavior of polyionic complex (PIC)membranes derived from polyvinyl alcohol(PVA) or ethylene-vinyl alcohol copolymer (EVA) have been investigated. The presence of ethylene block segment in the backbone of polyions can endow PIC membranes with more toughness. Increasing the degree of substitution of the polyions, the formed PIC becomes harder and more brittle. Under the environment of relative humidity (R. H. ) of 40%, the tensile strength, relative elongation and modulus of PICs are at about 300kg/cm²,10% and 8×10³kg/cm²,respectively,whereas inthe environment of 90% R.H.M these of PICs derived from EVA are at about 90 kg/cm²,150% and 13kg/cm²,respectively,better than that of PVA derived polyionic membrane and ordinary PIC such as Ioplex 101. The permeabil-ity of PIC membranes derived from EVA have also been studied.