由柔性配体庚二酸组装的微孔稀土配位高聚物

合成了3种新的庚二酸(H₂pim)稀土配位高聚物[Nd(Hpim)(pim)(H₂O)]_n·2nH₂O(1),[RE₂(pim)₃(H₂O)]_n·nH₂O[RE=Er(2),RE=Ho(3)],并通过元素分析红外光谱和单晶X射线衍射技术确定了其组成和晶体结构.配合物1为具有微孔的三维网状结构.配合物2和3同构,通过两种类型的O-H…O氢键将由配位键构筑的二维骨架结构组装成三维超分子结构.在这3个配合物中,庚二酸配体在同一配合物的结构中均存在不同的构象,体现了柔性配体不同于刚性配体的配位特点.     

1,10-菲啰啉-1-氧化物及乙酸与稀土的双核配合物

合成了1,10-菲哆啉-1-氧化物(PhenNO)的稀土配合物RE₂(PhenNO)₆(Ac)₂(ClO₄)₄·3H₂O(RE=Eu,Gd,Tb,Ho,Er,Yb;Ac=乙酸根),经元素分析确定了配合物的组成,探讨了配合物的组成和结构对荧光性质的影响.     

2-羰基丙酸(吡啶-4-甲酰基)腙稀土双核配合物的合成、表征及抗肿瘤活性

从2-羰基丙酸(吡啶-4-甲酰基)腙(H₂PPFH)合成了13种组成为RE₂(PPFH)₃·nH₂O(RE=La-Yb,n=2～3)的稀土腙固体配合物。通过红外、紫外、元素分析,电导及核磁共振谱等方法对其进行了表征。经药理实验发现配合物Eu₂(PPFH)₃·3H₂O具有抗肿瘤活性。     

二价稀土(Sm,Eu,Yb)与3-苯基-5-(呋喃-2)吡唑啉二硫代甲酸固态配合物的制备

本文首次制得了二价稀土与含硫有机配体的固态配合物RE(SSCNC₁₃H₁₁NO)₂·xH₂O(RE=Sm,Eu,Yb,x=3,4),研究了它们的性质,并对二价及相应的三价稀土配合物在物理化学性质上的差异进行了探讨。     

稀土-DBF-偶氮氯膦配合物极谱吸附波的研究

近年来稀土(RE)与变色酸偶氮类试剂的配合物极谱吸附波的研究已有若干报道^[1～3],其测定稀土的检测下限一般为10^-6-10^-7mol/L,有些体系可达10^-7～10^-8mol/L^[4]。DBF-偶氮氯膦(DBF-CPA)是一种新的变色酸双偶氮类稀土光度分析试剂^[5,6].该试剂具有选择性好、灵敏度优于其它试剂的特点.但RE(Ⅲ)-DBF-CPA配合物的电化学性质及其在极谱分析中的应用尚未见报道.本文发现在NH₄Cl介质中,RE(Ⅲ)-DBF-CPA配合物在滴汞电极(DME)上产生灵敏的极谱吸附波,利用该波测定稀土具有灵敏度高、稳定性好、线性范围宽等优点。其检出限可达1.4×10^-8mol/L。     

Keggin结构稀土钼钒磷四元杂多配合物的合成、表征及苯酚羟化制苯二酚的催化活性

合成了5种通式为(NH₄)₁₅[RE(PMo₉V₂O₃₉)₂]·xH₂O(RE=La³⁺,Ce³⁺,Gd³⁺,Y³⁺,Yb³⁺)的稀土钼钒磷四元杂多配合物,并用IR,UV,XRD,ICP,TG-DTA和CV等手段对其结构和性能进行了表征.催化活性实验表明,标题化合物对苯酚过氧化氢羟化制苯二酚反应有良好的催化活性.     

稀土硝酸盐冠醚配合物(ⅩⅥ)——冠醚B12C4与稀土硝酸盐配合物的合成与性质

在乙腈和丙酮中合成了冠醚B₁₂C₄与稀土硝酸盐的配合物RE(NO₃)·B₁₂C₄·xH₂O。通过金属离子的配位滴定、冠醚B₁₂C₄的分光光度测定、溶剂的气相色谱分析以及红外光谱、差热(DSC)与热重分析和X-射线衍射分析等方法研究了配合物的组成和性质。还在15±0.1℃测定了各配合物在乙腈中的溶解度。考察了重稀土(Tm、Yb和Lu)配合物1:1型向2:1型的转变。     

1-苯基-3-甲基-4-苯甲酰基吡唑酮-5稀土络合物的合成与表征

本文通过组成和物相分析证明按Roy和Okarfor的方法所合成的不是RE(PMBP)₃而是RE(PMBP)₃·HPMBP络合物。我们提出一种合成RE(PMBP)₃络合物的新方法,井用此法合成了45种稀土与HPMBP的固体络合物,对它们进行了组成分析,红外光谱和核磁共振谱等研究,其中有30种为新化合物。     

具有生物活性的金属配合物研究(Ⅶ)——对氨基水杨酸稀土配合物的合成、性质、抗结核菌及毒性研究

本文报道了14种对氨基水杨酸稀土配合物的合成,通过元素分析、红外光谱、紫外光谱、摩尔电导、差热分析、X射线粉末衍射等手段对配合物进行了性质测定,确定了该系列化合物的组成为RE(PAS)₃nH₂O(RE=La,Ce,Pr,Nd,Sm,Eu,Tb,Dy,Ho,Er,Tm,Yb,Lu,Y,PAS为对氨基水杨酸根,n=1～3)。红外光谱证明稀土元素与配体中的羧基和其邻部位的羟基形成稳定的六元螯合环。抗结核菌及抑菌毒性实验表明,稀土配合物的毒性比对氨基水杨酸钠的毒性小;抗结核菌的作用比对氨基水杨酸钠的作用略强。     

Eu(BSA)3phen与PVK共混体系的光致和电致发光特性的研究

合成了一类新型的以苯甲酰水杨酸(benzoyl salicylic acid,BSA)为第一配体,邻菲罗啉(1,10-phenanthroline,phen)为第二配体的稀土配合物Eu(BSA)3phen,将导电高分子材料PVK引入到配合物中,制成了结构为ITO/PVK:RE配合物/LiF/Al的电致发光器件.通过测量电致发光和光致发光光谱,发现PVK:RE配合物混合体系存在着能量传递,并对Eu(BSA)3phen与PVK共混体系的光致发光和电致发光机制进行了分析.同时比较了几种不同PVK掺杂浓度对于器件性能的影响.     

A 199Hg NMR spectroscopic study of two and three-coordinate methylmercury(II) complexes, [MeHgL]NO3

¹⁹⁹Hg NMR spectra are reported for the complexes [MeHgL]NO₃ containing either two- (e.g. L = pyridine) or three-coordinate mercury (e.g. L = 2,2′-bipyridyl). For unidentate and bidentate ligands of similar basicity chelation with bidentate ligands to give three-coordinate mercury results in upfield shifts of ¹⁹⁹Hg resonances from that of the linear complexes. For complexes of unidentate ligands shifts correlate with changes in base strength of the ligands, and methyl substitution in the 2 position of pyridine appears to result in an upfield shift of ca. 30 ppm. Effects of substitution in the 2 position are very strong in complexes of unidentate 2-benzylpyridine and 3,3′-dimethyl-2,2′-bipyridyl. Comparison of the ¹⁹⁹Hg shifts with J(¹H-¹⁹⁹Hg) shows the coupling constant to be insensitive to substitution in the 2 position in linear complexes and is a function only of the ligand base strength.     

Reactivity of [Re[kappa(3)-H(mu-H)B(tim(Me))(2)](CO)(3)] (tim(Me) = 2-mercapto-1-methylimidazolyl) toward neutral substrates

The complex [Re[kappa(3)-H(mu-H)B(tim(Me))(2)](CO)(3)] (2a) (tim(Me) = 2-mercapto-1-methylimidazolyl) reacts with a variety of neutral substrates to afford new complexes featuring the dihydrobis(2-mercapto-1-methylimidazolyl)borate coordinated in a bidentate or unidentate fashion. By treating 2a with unidentate ligands, the mononuclear complexes [Re[kappa(2)-H(2)B(tim(Me))(2)](CO)(3)(L)] (L = imidazole (5), 4-(dimethylamino)pyridine (6), tert-butylisonitrile (7), triphenylphosphine (8)) were formed, upon replacement of the agostic B-H...Re bond by the correspondent unidentate ligand. With potentially bidentate substrates, 2a is transformed into mononuclear or dinuclear complexes, depending on the atom donor set of the reacting substrates. Reaction of compound 2a with ethylenediamine (en) gave the complex [Re[kappa(1)-H(2)B(tim(Me))(2)](CO)(3)(en)] (9), because of cleavage of the agostic interaction, dechelation of one mercaptoimidazolyl ring, and bidentate coordination of the amine. By contrast, 1,2-bis(diphenyl)phosphinoethane (dppe) is not able to replace the mercaptoimidazolyl ring, and the dimer [Re[kappa(2)-H(2)B(tim(Me))(2)](CO)(3)](2)(mu-dppe) (10) was formed. The novel Re(I) tricarbonyl complexes (5-10) have been fully characterized, including by X-ray diffraction analysis in the case of 6, 8, 9, and 10. The X-ray diffraction study confirmed the unprecedented unidentate coordination mode of the dihydrobis(2-mercapto-1-methylimidazolyl)borate in complex 9.     

Synthesis and structural characterization of lanthanide picrate complexes with a new binaphthylamide

Solid complexes of lanthanide picrates with N-Ethyl-2-{2′-[(ethyl-phenyl-carbamoyl)-methoxy]-[1,1′]binaphthalenyl-2-yloxy}-N-phenyl-acetamide (L), [Ln(pic)₃L] (Ln=La, Tb, Y), have been prepared and characterized by elemental analysis, IR and ¹H NMR spectra. The molecular structure of [Tb(pic)₃L] shows that the Tb(III) ion is nine-coordinated by four oxygen atoms from the L and five from two bidentate and one unidentate picrates. The complex forms a 1D supramolecular structure along z-axis.     

ADDUCTS OF THEOBROMINE WITH 3d METAL PERCHLORATES

Abstract

Adducts of theobromine (tbH) with 3d metal perchlorates (Mⁿ⁺ = Cr^3-. Mn²⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn^2- I here prepared by refluxing mixtures of the Iigand and a metal salt in ethyl acetate-triethyl orthoformate. The new complexes invariably involve 2: 1 molar ratios of tbH to metal ion and are apparently monomeric with terminal tbH ligands binding riaa ring nitrogen (N9 or Nl). The Mn²⁺, Cu²⁺ and Zn^2- complexes are distorted tetrahedral, involving tuo tbH and two unidentate perchlorato ligands in the first coordination sphere of the metal ion. The remaining metal(II) complexes (Fe, Co, Ni) were obtained as monohydrates. These compounds are pentacoordinated of the [M(tbH)₂(OClO₃)₂(OH₂)] type, containing one aqua ligand in addition to the tbH and perchlorato ligands. The Cr³⁺ and Fe³⁺ complexes are low-symmetry hexacoordinated, with two tbH ligands. two unidentate and one bidentate chelating perchlorate Iigands.     

Synthesis and structural characterization of lanthanide(III) nitrate complexes of a tetraiminodiphenol macrocycle in the solid state and in solution

The lanthanide(III) complexes [Ln(LH2)(NO3)3] 1-11(La-Er), 15(Y) and [Ln(LH2)(NO3)2(H2O)](NO3) 12-14 (Tm-Lu) of the tetraiminodiphenolate macrocycle L2- have been prepared by the transmetallation reaction between [Pb(LH2)(NO3)2] and Ln(NO3)3.nH2O. In these compounds, the uncoordinated imino nitrogens are protonated and are hydrogen bonded to the phenolate oxygens. The X-ray crystal structures of the La (1), Ho (10) and Lu (14) compounds have been determined. Compounds 1 and 10, in which all the three nitrates are bound in bidentate fashion, are isostructural with distorted bicapped square antiprism geometry for the metal centre. In [Lu(LH2)(NO3)2(H2O)](NO3) 14, of the two metal bound nitrates one is bidentate and the other is unidentate, while the metal centre obtains a distorted square antiprism coordination environment. Proton NMR spectra of the paramagnetic lanthanide complexes have been studied in detail. Contributions of contact and pseudo-contact shifts to the lanthanide induced isotropic shifts (LIS) of the macrocycle protons have been separated and good agreement has been obtained between the calculated LIS values and the experimentally observed values. Analysis of the NMR data has led us to conclude that all the complexes in dimethyl sulfoxide solution attain similar configurations. The absorption and emission spectral characteristic of several compounds have been investigated. The complexes of samarium (5) and europium (6) on photoexcitation at 400 nm exhibit well-resolved luminescence spectra at 77 K both in the solid state and a methanol-ethanol (1 : 4) glassy matrix. For the terbium (8) and dysprosium (9) complexes, however, the observed luminescence peaks are less resolved and weak in intensity.     

氨噻肟酸稀土配合物的合成、抗氧化性及抗菌活性的研究

合成了１２种稀土氨噻肟酸（ＨＬ）固体配合物,其通式为ＲＥＬ３（ＲＥ＝Ｌａ,Ｃａ,Ｐｒ,Ｎｄ,Ｓｍ,Ｅｕ,Ｇｄ,Ｔｂ,Ｅｒ、Ｔｍ,Ｙｂ,Ｙ）。利用元素分析、红外光谱、核磁共振氢谱、摩尔电导、热分析等测试手段对配合物进行了表征,研究了ＮｄＬ３、ＥｒＬ３配合物在ＤＭＳＯ溶液中电子吸收光谱,计算了电子云伸效应参数β,共价参数　和键合参数ｂ＾１／２,讨论了配合物的共价成键情况,并对其抗氧化及抗菌活性做了研究     

Pyrazine as a building block for molecular architectures with PtII

A series of pyrazine (pz) complexes containing cis-(NH(3))(2)Pt(II), (tmeda)Pt(II) (tmeda = N,N,N',N'-tetramethylethylenediamine), and trans-(NH(3))(2)Pt(II) entities have been prepared and characterized by X-ray crystallography and/or 1H NMR spectroscopy. In these compounds, the pz ligands act as monodentate (1-3) or bidentate bridging ligands (4-7). Three variants of the latter case are described: a dinuclear complex [Pt(II)]2 (4b), a cyclic tetranuclear [Pt(II)](4) complex (5), and a trinuclear mixed-metal complex [Pt2Ag] (7). Mono- and bidentate binding modes are readily differentiated by 1H NMR spectroscopy, and the assignment of pz protons in the case of monodentate coordination is aided by the observation of (195)Pt satellites. Formation of the open molecular box cis-[{(NH3)2Pt(pz)}4](NO3)8.3.67H2O (5) from cis-(NH3)2Pt(II) and pz follows expectations of the "molecular library approach" for the generation of a cyclic tetramer.     

Thermal stability of new biologic active copper(II) complexes with 5,6-dimethylbenzimidazole

Three new coordinative compounds that contain mixed ligands (5,6-dimethylbenzimidazole and acrylato anion) were synthesized and characterized. The features of complexes have been assigned from microanalytical, IR, UV–Vis and EPR spectra as well as thermal analysis. IR data are in accordance with unidentate nature of 5,6-dimethylbenzimidazole while the acrilato ion acts as uni- or bidentate ligand. The electronic spectra display the characteristic pattern of square pyramidal or octahedral stereochemistry, which were confirmed by the EPR spectra. Antibacterial and antifungal activities of the complexes have been determined in vitro, against various Gram-negative and Gram-positive bacteria and fungi. The tested complexes exhibited different spectra of antimicrobial activity and inhibited the microbial ability to colonize the inert surfaces, acting as potential anti-adherence and biofilm-controlling agents. Thermal decomposition evidenced several well-defined steps as dehydration (complex 2), 5,6-dimethylbenzimidazole molecule release (all complexes) and the acrylate decomposition in carbonate (complex 3). The final residue is in all cases copper (II) oxide.     

Synthesis and characterization of peroxo complexes of uranium(VI) with aroylhydrazone ligands

The uranium(VI) peroxo complexes containing aroylhydrazones ligands having composition [UO(O₂)L-L(NO₃)₂]·H₂O (where L-L = Benzoic acid[1-(Furan-2-yl)methylene] hydrazide, Benzoic acid[(thiophene-2-yl)methylene] hydrazide, Benzoic acid[1-(thiophene-2-yl)ethylidene] hydrazide, Benzoic acid(phenylmethylene) hydrazide, Benzoic acid[1-(anisol-3-yl)methylene] hydrazide and Benzoic acid[(p-chlorobenzyl)methylene] hydrazide are reported. The complexes were characterized by various physico-chemical techniques, viz. elemental analysis, molar conductivity, magnetic susceptibility measurements, infra red, electronic, mass spectral and TGA/DTA studies. These studies revealed that complexes are non-electrolytes and diamagnetic in nature. The ligands are bound to metal in a bidentate mode. Thermal analysis results provide conclusive evidence for the presence of water molecules in the complexes. Mass spectra confirm the molecular mass of the complexes. Antifungal activity of complexes revealed enhanced activity of complexes as compared to the corresponding ligands.     

含硫过渡金属基元的反应 2: 双膦及双齿巯基混合配位钴, 镍化合物的合成和结构特征

双膦(P-P)和1, 2-双齿巯基(S-X)混合与MCl2(M=Co, Ni)反应,得到通式为M(S-X)(P-P)的产物。晶体结构测定表明, 配合物Co(bdt)(dppe)(1), Ni(tdt)(dppm)(2)和Ni(tsal)(dppe)(3)中的金属均为SXP2配位的四方平面构型, S, X, P原子分别来自二种双齿配体, 各形成四、五或六元螯合配位环。文中总结了结构特征, 探讨了基元配合物稳定的原因。