SYNTHESES,CRYSTAL STRUCTURES AND ELECTRONIC SPECTRA OF MIXED-LIGAND ZINC(II) COMPLEXES WITH DIIMINES AND DITHIOLATES

Abstract

Three zinc(II) complexes, [Zn(bipy)(dmit)]₂ (1), [Zn(phen)(dmit)]₂ (2) and Zn(py)(mnt) (3), where bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline, py = pyridine, H₂dmit = 4,5-dimer-capto-1,3-dithiol-2-thione, mnt = maleonitriledithiolate, have been synthesized and their crystal structures determined. Complex 1 is monoclinic, space group P2₁/c, with a = 11.570(3), b = 9.137(3), c = 15.051(6)Å, β = 109.56(2)°, Z = 2 and was refined to R ₁ = 0.039. Complex 2 is monoclinic, space group P2₁/n, with a = 9.363(2), b = 13.732(3), c = 12.767(3), β = 94.06(3)°, Z = 2 and was refined to R ₁ = 0.038. Complex 3 is orthorhombic, space group P2₁2₁2₁, with a = 8.621(3), b = 10.546(4), c = 16.848(2), Z = 4 and was refined to R ₁ = 0.040. IR and electronic absorption spectra were investigated.     

SYNTHESES,CRYSTAL STRUCTURES AND ANTIBACTERIAL ACTIVITIES OF MONONUCLEAR NICKEL(II) COMPLEXES WITH SIMILAR SCHIFF BASES

Journal of Structural Chemistry - Two mononuclear nickel(II) complexes, [Ni(L1)2] (1) and [Ni(L2)2] (2), where L1 and L2 are the anions of 4-methylbenzoic acid (1-pyridin-2-ylmethylidene)hydrazide...     

CRYSTAL STRUCTURES AND TRIBOLUMINESCENT ACTIVITIES OF SAMARIUM(III) COMPLEXES

Abstract

The triboluminescence spectra and crystal structures of 1,2-dimethylpyridinium tetrakis(2-thenoyltrifluoroacetonato)samarium(III) (1) and 1,2,6-trimethylpyridinium tetrakis(2-thenoyltrifluoroacetonato)samarium(III) (2) were determined. The triboluminescent maximums are similar to those of the photoluminescence. Complex 1 is centrosymmetric and the triboluminescent emission may correlate with the disorder of all S atoms, all CF₃ groups and the cation. The triboluminescent activity of complex 2 may correlate with its noncentrosymmetric space group. Complex 1 crystallizes in the monoclinic space group P2₁/a with cell parameters a = 19.874(2) Å, b = 22.922(2)Å, c = 21.188(1)Å, β = 108.126(6)°, V = 9173(1)ų; Z = 8; R = 0.0758 and R_w = 0.1315. Complex 2 crystallizes in the monoclinic space group Pn with cell parameters a = 11.2808(6)Å, b = 11.0199(5)Å c c = 18.4336(9)Å, β = 108.126(6)° V = 2285.28(19)ų; Z = 4; R = 0.0347 and R_w = 0.0900. All the structures were refined by full-matrix least squares methods.     

反丁烯二酸稀土配合物的合成及晶体结构

合成了反丁烯二酸C_4H_4O_4与六种稀土(Eu, Gd, Tb, Y, Er, Lu)的配合物M_2F_3·12H_2O(H_2F=C_4H_4O_4). 用X射线衍射法测定了它们的晶体学参数, 并测定了其中五种配合物的结构. 指出存在两类不同的结构, 其中铕配合物为三斜晶系, 空间群P(1), 铕离子配位数为10. 铽、钇、铒、镥配合物为单斜晶系, 空间群为P2_1/c, 配位数为8. 配合物均具有三维网状结构.     

STUDIES ON SYNTHESES,CRYSTAL STRUCTURES,DFT CALCULATION AND ANTI-BREAST-CANCER ACTIVITIES OF ARTEMINSIN-PURINE HYBRIDS

Journal of Structural Chemistry - A pair of C9-C10-trans-C10-artemisinin-purine hybrids (A and B) were stereoselectively synthesized under a protonic acid condition, which were structurally...     

邻羟基苯甲酸希土配合物的合成及晶体结构

本文合成了邻羟基苯甲酸(o-HOC_6H_4CO_2H)与十五种希土的配合物,测定了铈,铽的配合物晶体结构。二者均属单斜晶系,铈配合物空间群为P2_1/n。配位数为9,铽配合物空间群为Cc,配位数为8.两种配合物均呈无限链状聚合结构。     

SYNTHESES,CHARACTERIZATION AND CRYSTAL STRUCTURE OF TETRAMETHYLDIBENZOTETRAAZA[14]-ANNULENE ZINC(II) COMPLEXES CONTAINING AN AXIAL BASE

Abstract

The complexes of Zn(tmtaa) and Zn(tmtaa)L [H₂tmtaa = tetramethyldibenzotetraaza[14]-annulene; L = triethylamine, pyridine (Py) and p-dimethylaminopyridine (p-N(CH₃)₂Py)] were synthesized and characterized by IR, LTV, mass and NMR spectra as well as DSC measurements. The effects of different axial ligands (L) on the spectral properties of the complexes have been studied. The crystal structure of Zn(tmtaa)N(C₂H₅)3 was determined by X-ray diffraction. The crystal belongs to a monoclinic system and the space group is P2₁/n. The cell parameters are a = 11.134(2)A, b = 17.453(4)Å, c= 13.784(3)Å, ? = 106.19(3)°, Z = 4, R₁, =0.0336 and wR₂= 0.0805 for 4539 independent reflections with I <2σ(I). The zinc(II) is coordinated through four nitrogen atoms of tmtaa and a nitrogen of triethylamine to form a five-coordinate square-pyramidal structure. The average bond length of Zn for the four nitrogens of tmtaa is 2.050(2)Å and for a nitrogen of triethylamine is 2.188(2)Å. The displacement of the zinc to the plane of four nitrogens of tmtaa is 0.563(2)Å.     

SYNTHESES AND CRYSTAL STRUCTURES OF ISOMALONONITRILE DITHIOLATO COMPLEXES (Bu4N)2Zn(i-mnt)2 AND (Et4N)2Pd(i-mnt)2

Abstract

Two isomalononitrile dithiolato complexes, (Bu₄N)₂Zn(i-mnt)₂ (1) and (Et₄N)₂Pd(i-mnt)₂ (2) were synthesized and characterized by elemental analysis, IR and electronic spectroscopy. Their structures have been crystallographically determined. The reaction of (Et₄N)₂Pd(i-mnt)₂ (2) with (Et₄N)₂WS₄ gives (Et₄N)₂WS₄Pd(i-mnt).     

SYNTHESIS,CRYSTAL STRUCTURE AND ANTIMICROBIAL ACTIVITY OF COBALT(III) COMPLEXES WITH SCHIFF BASE LIGANDS

Journal of Structural Chemistry - Three new mononuclear cobalt(III) complexes, [CoL1(4-Brsal)] (1), [CoL3(4-Brsal)] (2), and [Co(L2)2]NO3 (3), where L1, L2, L3 and 4-Brsal are the deprotonated form...     

SYNTHESES AND CRYSTAL STRUCTURES, REACTION OF α -THIOPI-COLIN-o-TOLUIDIDE AND ITS ORGANOTIN COMPLEX

<正> α-thiopicolin-o-toluidide and its organotin complex have been synthesized, and both crystal structures have been determined by X-ray analysis. The ligand:C13 H12N2S,Mr = 228. 3,monoclinic,P21/n,a=16. 387(1),b = 7. 752(2),c=18. 334(1) A ,β=95. 52(1),V = 2324. 8A3,Z = 8,DC=1. 305g·cm-3,F(000) = 960e. The final R= 0. 053 for 3291 observed unique reflections. There are two molecules in the asymmetric unit,which are confirmed to exist as the keto,cis-N configuration in the solid state. The complex:C17H21N2SClSn,Mr = 439. 6,orthorhombic,P212121,a = 8. 801(3),b = 9. 188 (2),c=24. 087(6) A,V=1947. 9A3,Z = 4,DC=1. 499g·cm-3,F(000) = 880e. The final R = 0. 041 for 1694 observed unique reflections. The tin atom is surrounded by an irregular (5 + 1) coordination geometry with five normal bonds and one weak bond [Sn....C1]. The molecules join each other through the weak bonds to form infinite polymeric chains parallel to the a axis. In addition, the possible reaction mechanism in coordination is discussed.     

基于2,5-二(4-氨基苯)嘧啶聚酰亚胺的合成及性能表征

1,5-二氮杂戊二烯盐(vinamidium salts)与4-硝基苯甲脒盐在碱性物质的存在下发生成环反应得含嘧啶环的硝基化合物;硝基化合物用Pd/C和水合肼还原得到棒状含氮芳杂环二胺——2,5-二(4-氨基苯基)嘧啶.通过1H-NMR,13C-NMR,IR,MS及元素分析确证了含氮芳杂环二胺及其中间产物的结构.这种二胺或加一定量对苯二胺与均苯二酐(PMDA)或联苯二酐(BPDA)通过两步法聚合获得一系列聚酰亚胺,通过红外、动态力学、静态力学、热重分析、广角X射线衍射等实验测试了该类聚合物的结构、热性能、机械性能及结晶性能.     

二[1,2-二硫代(3,5-二硫杂-4-硫酮)戊烯]铜和锌络合物的四丁基胺盐的晶体结构

1,2-二硫代烯基(1)和1,2-二硫代苯基(Ⅱ)类型的金属络合物的研究,已有很多报道。但Ⅰ和Ⅱ与Zn的络合物的晶体结构至今未见报道。Gray等人发现在[N(C_4H_8)_4]_2[M′(MNT)_2]络合物的X射线粉末图中,Co,Pt,Ni络合物的衍射花样完全相同,但Zn络合物的确有明显的不同。Billig等人在[N(C_2H_5)_4]_2[M″(MNT)_2](M″=Cu,Ni,Zn)络合物的X射线粉末花样中也观察到同样的现象。他们认为Zn络合物为四面体的构型,但未测定其结构。近来,Lindqvist又推出一种1,2-二硫代(3,5-二硫杂-7-硫酮)戊烯基(Ⅲ)新的配位体。为了解Cu,Zn与Ⅲ形成络合物的特征,本文测定了标题络合物的晶体结构。     

NICKEL(II) COMPLEXES OF TRIDENTATE N,N,O-DONOR LIGANDS: SYNTHESES,STRUCTURES AND REDOX PROPERTIES

Abstract

Nickel(II) complexes ([NiL₂]) of tridentate Schiff bases (HL) containing amide functionality are described. The Schiff bases, Hpabh and Hpamh (H refers to the dissociable amide proton), are derived from 2-pyridinecarboxaldehyde and benzhydrazide, and 2-pyridinecarboxaldehyde and 4-methoxybenzhydrazide, respectively. The reaction of two equivalents of HL and one equivalent of Ni(O₂CCH₃)₂ · 4H₂O in methanol affords [NiL₂] in high yield. The complexes are characterised by analytical, spectroscopic, magnetic and electrochemical techniques. The structures of both complexes have been determined by X-ray crystallography. The distorted octahedral NiN₄O₂ sphere in each complex is assembled by the two meridional N,N,O-donor ligands. Each ligand binds the metal ion via the pyridine-N, imine-N and deprotonated amine-O atoms. The solid state room temperature (298 K) magnetic moments are consistent with a d ⁸ (S = 1) ground state electronic configuration. Electronic spectra of the complexes in CH₃CN solutions display the v ₁ band at ～ 850 nm followed by charge transfer bands in the range 381–241 nm. The [Ni^IIIL₂]⁺-[Ni^IIL₂] couple was observed in the cyclic voltammograms of both complexes. The potentials are 0.97 and 0.91 V (versus Ag-AgCl) for [Ni(pabh)₂] and [Ni(pamh)₂], respectively.     

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.     

CRYSTAL STRUCTURES OF MIXED-LIGAND BINUCLEAR Zn(II) 2-IODOBENZOATE COMPLEXES WITH 4-ETHYL- AND 3-CHLOROPYRIDINE

Journal of Structural Chemistry - Reactions of Zn(NO3)2·6H2O, 2-iodobenzoic acid (2-IBA), and 4-ethyl- or 3-chloropyridine result in the formation of binuclear neutral complexes...     

SYNTHESES AND MOLECULAR STRUCTURES OF THE ASYMMETRICAL DIPHOSPHINE LIGANDS AND THEIR Pt, Ni ORGANOMETALLIC COMPLEXES

In this paper, we report a novel two-step synthetic method of the symmetrical and asymmetrical diphosphine ligands 1, 2-bis(ditertbutylphosphino)ethane and 1, 2-bis(phenyltertbutylphosphino) ethane, and simultaneously establish a novel synthetic method of diphosphine ligand 1, 4-bis(phosphinocyclopentyl)butane with larger chelate ring. The former was prepared from the reaction of 1, 2-bis(dichlorophosphino)ethane with Grignard reagent andalkyl lithium, respectively, the latter from the reaction of 1, 4-di-Grignard reagent with PCl_3. Furthermore, a series of organometallic complexes of Pt, Ni containing diphosphine chelate ligand were prepared from the reaction of (COD) PtCl_2 complex with diphosphine. These complexes are very stable. Among these complexes, the molecular structures of (d(t-Bu)pe)-PtCl_2, (dPCypb)PtCl_2 and ((n-Bu) (PCyp))_2PtCl_2 complexes have been determined by X-ray diffraction method indicating they are novel complexes. The influence of diphosphine ligand on the molecular structure     

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。     

STRUCTURE OF COMPOUNDS DERIVED FROM [Au(Dien)Cl]Cl2 AND PLATINUM CHLORIDE COMPLEXES

Journal of Structural Chemistry - Double complex salts [Au(Dien)Cl][PtCl4]·H2O (1) and [Au2(Dien*)Cl4]2[PtCl6]·2H2O (2), where Dien* is diethylenetriamine with a deprotonated imino group,...     

四（烷硫基苯基）卟啉及其金属配合物的合成

某些人工合成的金属卟啉,由于其活化分子氧的功能,被广泛用作生物模拟氧化反应中的催化剂。金属四苯基卟啉及其衍生物是用得最普遍的模型化合物。文献中巳报道过各种四苯基卟啉衍生物的合成方法,但尚未见带烷硫基的四苯基卟啉衍生物的系统合成方法。本文报道这类四苯基卟啉衍生物及其金属配合物的合成。 本文采用通常的一步法合成四苯基卟啉衍生物,即首先参照文献方法合成烷硫基苯甲