SYNTHESIS AND CHARACTERIZATION OF METAL COMPLEXES WITH AMPICILLIN

Abstract

The reaction, in water, of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) ions with sodium ampicillinate at room temperature has allowed isolation of dimers with the following general formula [M(amp)Cl]₂ × nH₂O (n = 1.5?3.2). The complexes were characterized by elemental analyses, conductivity measurements, magnetic susceptibilities and spectroscopic methods (IR, Raman, EPR and UV-Visible). A dinuclear structure based on octahedrally coordinated metal ions is proposed.     

SYNTHESIS,CHARACTERIZATION AND STRUCTURAL ANALYSES OF THREE LANTHANIDE CYANIDE-BRIDGED COMPLEXES

Abstract

Three lanthanide (Ln) complexes (DMF)₄(H₂O)₃LnFe(CN)₆ · H₂O, where Ln = Er, Yb, and Lu, were structurally determined by means of three-dimensional single-crystal X-ray diffraction analysis. These systems crystallize in the centrosymmetric monoclinic space group P2₁/c (No. 14) with Z = 4 and respective lattice constants of a = 13.956(2), 13.952(1), 13.937(3); b = 8.867(4), 8.864(1), 8.862(2); c = 24.857(3), 24.812(2), 24.770(5) Å; and β = 96.30(1)°, 96.33(1)°, 96.30(3)°. Final least-squares full-matrix refinements based on 3499, 3367, and 2555 unique reflections yielded reliability (R) index factors of 0.071, 0.051, and 0.032, respectively. In each complex, the coordination about the central Ln ion is eight in a square-antiprism arrangement and the coordination about the Fe ions is six, oriented octahedrally. Cyanide bridging links the Ln ions to the FeC₆ groups. Molecules in the crystal lattice of each complex are held together by van der Waals forces and a network of hydrogen bonding. Characterization includes physical property determinations, conoscopical studies, thermal gravimetric analyses, and IR spectrometric identifications. Selected bond lengths and angles are tabularized and a synthesis of these compounds is presented.     

还原席夫碱型三角架式金属配合物的合成和性质研究

由2，2，′，2＂-三氨基三乙胺(tren)与N-氧化吡啶醛经席夫碱型缩合，然后还原C=N双键形成的产物为配体(L¹)，合成了一系列新三角架式过渡金属配合物：［ML¹］²⁺［M=Mn(Ⅱ)、Ni(Ⅱ)和Zn(Ⅱ)］。利用元素分析、红外光谱、电子光谱和室温磁化率对配合物的结构和性质进行了研究。     

杂环息夫碱化合物及其过渡金属配合物的合成与表征

本文合成了一种新的双齿(N,O)杂环息夫碱2-(2′-羟基)苯甲亚胺-5-(4′-硝基)偶氮苯吡啶(HL)与过渡金属的六种新配合物ML_2及M′L_3 [M=Mn(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)、Pd(Ⅱ);M′=Fe(Ⅲ)].采用元素分析、摩尔电导、红外光谱、紫外—可见光谱、磁化率以及热分析等研究了配合物的组成和性质.     

二(1,3-二硫杂环戊烯-2-硫酮-4,5-二巯基)镉-季铵类配合物的合成与表征

二（１，３－二硫杂环戊烯－２－硫酮－４，５－二巯基）镉－季铵类配合物的合成与表征李洪启宋燕西＊周宏英王爱勤姚钟麒俞贤达（中国科学院兰州化学物理研究所，兰州７３００００；＊兰州大学化学系，兰州７３００００）关键词二（１，３－二硫杂环戊烯－２－硫酮－４，...     

聚酯型Gd(Ⅲ)配合物的合成与表征

将二乙三胺五乙酸双酐与五种分子量不同的聚乙二醇共缩聚，制得聚酯型大分子配体，配体与ＧｄＣｌ３·６Ｈ２Ｏ反应，生成相应的配合物，并测试了配合物的弛豫速率．结果表明这些配合物比现用于临床的磁共振成像造影剂Ｇｄ（ＤＴＰＡ）具有更高的弛豫速率．     

铜(Ⅱ)5-氟尿嘧啶的多核配合物的合成及磁学性质表征

本文合成了两种新的铜(Ⅱ)5—氟尿密嘧啶配合物,[Cu(fuH)(Ac)(OH)](1)和[Cu_3O(fuH)_2(Ac)(OH)_3](2),进行了元素分析和红外光谱测定。从80-300K变温磁化率的数据表明,1和2均服从Curie-Weiss定律,θ值分别为-92K和-94K,证示在1和2分子内部均存在着反铁磁偶合作用。出1的室温多晶EPR谱测得g‖=2.30,g⊥=2.08和|A‖|=16.8mT,表明铜(Ⅱ)的几何构型为畸变四方形,其单电子主要集居于d_(x~2-y~2)轨道。同时对1和2的可能结构及反铁磁偶合作用机制进行了讨论。     

SYNTHESIS AND CHARACTERIZATION OF TRIS(ALKYLISOCYANIDE) BIS(TRIARYL-PHOSPHINE)COBALT(II) COMPLEXES

Abstract

A series of complexes having the general formula, [Co(CNR)₃(PR₃)₂]X₂, X = ClO₄, BF₄ with CNR = CNCMe₃, CNCHMe₂, CNC₆H₁₁. CNCH₂Ph and PR₃ = PPh₃, P(C₆H₄Me-p)₃, P(C₆H₄OMe-p)₃ has been synthesized and characterized. Synthesis can be achieved by reaction of [Co(CNR)₄(AsPh₃)₂]X₂ complexes with controlled excess of PR₃ ligands, and by AgClO₄/AgBF₄ oxidation of the [Co(CNR)₃(PR₃)₂]X complexes. The latter procedure is preferable. Alternate syntheses of the [Co(CNR)₃(PR₃)₂]X complexes have also been employed. Five-coordinate Co(II) complexes have not been obtained using CNCMe₃ with P(C₆H₄Me-p)₃ ligands, CNCH₂Ph with P(C₆H₄OMe-p)₃ ligands, or CNC₄H_9-n with PPh₃ ligands. [Co(CNC-Me₃)₃{P(C₆H₄Cl-p)₃}₂]ClO₄ produced only [Co{CNCMe₃)₄H₂O](ClO₄)₂ upon forced oxidation with excess AgClO₄. [Co(CNR)₃(PR₃)₂]X₂ complexes appear to undergo varying degrees of distortion from regular (i.e., D _3h symmetry) axially-disubstituted trigonal bipyramidal coordination in the solid state, as evidenced by v(-N°C) IR patterns, but to assume regular trigonal bipyramidal coordination in solution. Effective magnetic moments indicate one-electron paramagnetism, and solution electronic spectra are compatible with trigonal bipyramidal coordination.     

SYNTHESIS, CHARACTERIZATION AND CATALYTIC BEHAVIOR OF DIMERIC Co(II) AND Ni(II) COMPLEXES CONTAINIGN N,N'-(PHENYL-2-PYRIDINYLMETHYLENE)-3,3',5,5'-TETRAMETHYLBENZIDINE

The N,N'-(phenyl-2-pyridinylmethylene)-3,3',5,5'-tetramethylbenzidine and its dimeric Co(II) and Ni(II) complexes were synthesized.The organic compound was characterized by elemental analyses,IR and NMR spectra,while the bimetal complexes were determined by elemental analyses,IR spectra as well as the single-crystal X-ray diffraction.The nickel complex showed high activity for ethylene polymerization and its cobalt analogue showed negligible active in ethylene activation.     

大分子聚酯配体及其钆（Ⅲ）配合物的合成和核磁弛豫性能研究

通过二乙三胺五乙酸二酐（ＤＴＰＡＡ）分别与Ｎ－正丁基、正辛基、苄基、对甲苯磺酰基、苯基和对溴苯基取代二乙醇胺共聚，制得一系列大分子配体及其钆（ＩＩＩ）配合物．对所合成的配体和钆配合物进行了表征，并测试了部分钆配合物的核磁弛豫性能．     

若干锰(Ⅲ)希夫碱配合物的合成和表征

合成了六种锰(Ⅲ)希夫碱配合物:Mn(bzacem)X(X~-=Cl~-,Br~-,I~-,NCS~-,NO_2~-)和Mn(bzacen)ClO_4·2H_2O,其中bzacen~(2-)为N,N′-二(苯甲酰丙酮缩)-乙二胺阴离子.用NMR法测定配合物在DMSO溶液中的有效磁矩值为4.46—4.63,表明为高自旋配合物,将电子光谱中的吸收带分别按配位场带、荷移带和配体带进行了归属,在配合物的红外光谱中,原配体H_2bzacen中的ν_(N-H)带消失,ν_(C-O)带移向低频,并对Mn-O、Mn-N和Mn-X的伸缩带进行了归属。     

苯甲酰丙酮缩乙二胺与镧系元素多核配合物的合成及表征

本文合成了8个镧系元素与苯甲酰丙酮缩乙二胺希夫碱配合物。经元素分析、摩尔电导、热分析、电子光谱、红外光谱与¹H NMR等表征,确证为双核配合物:Ln₂(L)₃(NO₃)₆·2H₂O(Ln=La、Ce、Pr、Nd、Sm、Gd、Dy及Er;L=苯甲酰丙酮缩乙二胺)。文中探讨了配体空间位阻等影响,并提出了所合成配合物的可能结构。     

镧系金属杂—2,3,4,5—四苯基环戊二烯环状化合物的合成及其表征

二苯乙炔和金属锂在乙醚中反应得到1,4-二锂四苯基丁二烯,再与无水氧化希土反应得到了两种系金属条-2,3,4,5-四苯基环戊二烯环状化合物。通过元素分析、红外光谱、核磁共振谱、热失重及电子能谱的分析,对所合成的化合物进行了表征;并对化合物的水解产物作了红外光谱、质谱和核磁共振谱分析,确认下列两种化合物的存在:     

SYNTHESIS AND CHARACTERIZATION OF POLYMER DERIVATIVES OF cis-PLATINUM COMPLEXES

Cis-platinum complexes used as antitumor drugs were attached onto preformed polymers toreduce the toxicity. Either alternating copolymer of styrene and maleic anhydride (CPSMA) orpolyacrylic acid (PAA) is readily dissolved in alkaline solution. The cis-platinum complexes areeasily converted into water soluble species when treated by silver nitrate in water. The expectedproducts could be obtained when the two aqueous solutions were brought together. The productswere characterized by elementary analysis, IR and XPS. The polymer derivatives could exchangeligands with nucleophilic groups in biological environment and also exhibit antineoplastic activity.     

噻吩甲酰基吡唑啉酮缩乙二胺配合物的合成、表征及生物活性

A new ligand N,N′-bis［(1-phenyl-3-methyl-5-oxo-4-pyrazolinyl)-2-thenoylmethylidyne］ethyl-enediimine (HPMTHP)₂en and its five complexes have been sythesized. These complexes have the general formula ［M(PMTHP)₂en］, where M=Cu(Ⅱ), Ni(Ⅱ)     

端三吡啶基聚异丙基丙烯酰胺的合成及其金属配合物

合成出三吡啶官能化的二硫代酯并以其作为链转移剂进行了异丙基丙烯酰胺(NIPAAm)的可逆加成断裂链转移(RAFT)聚合,得到分子量可控和窄分子量分布的端三吡啶基聚异丙基丙烯酰胺(tpy-PNIPAAm),聚合反应为对单体浓度的一级动力学关系.Tpy-PNIPAAm在水中既保持了与聚异丙基丙烯酰胺类似的相转变行为,又拥有三吡啶(tpy)的强络合能力.将tpy-PNIPAAm与金属核素模型进行络合得到金属配合物,所得金属配合物在水中拥有与PNIPAAm类似的相转变行为,同时tpy-PNIPAAm的金属配合物由于其两亲性,在水中可以形成纳米粒子,由于纳米粒子间的静电排斥作用,这种纳米粒子即使在高于相转变温度时,仍能稳定于水中.