Preparation and Catalytic Properties of Polymer-Bound Schiff Base Ternary Complexes

The polymer-bound Schiff base ternary manganese complexes [PS-SalPhe-Mn-L (L = Phen, Bipy and 8HQ)] have been prepared from the polymer-bound Schiff base ligand, a manganese salt and the second ligand, such as 1,10-phenanthroline (phen), 2,2‘-bipyridyl (bipy) and 8-quinolinol (8HQ). The polymer-bound Schiff base ternary manganese complexes were characterized by means of infrared spectrometry and ICPAES. The catalytic activities of the complexes have been studied in the aerobic epoxidation of long-chain linear aliphatic olefins. It is shown that 1-octene or 1-decene can be directly oxidized by molecular oxygen when catalyzed by PS-SalPhe-Mn-L(L=Phen, Bipy and 8HQ), and 1,2-epoxy alkane can be afforded in these reactions.     

Mononuclear and Dinuclear Cobalt Complexes and its Dioxygen Adduct with a New 24-membered Hexaaza Macrocyclic Ligand

Abstract

Dinucleating 24-membered hexaazadiphenol macrocyclic ligand 3,6,9,17,20,23-hexaaza-29,30-dihydroxy-13,27-dimethyl-tricyclo[23,3,1,1^11,15] triaconta-1(29), 11,13,15(30),25,27-hexaene (L or BDBPH), is prepared by the NaBH₄ reduction of the Schiff base obtained from [2+2] template condensation of 2,6-diformyl-p-cresol with diethylenetriamine. The ligand maintains dinuclear integrity for cobalt (II) while facilitating the formation of bridging phenolate dicobalt cores. Potentiometric equilibrium studies indicate that a variety of protonated, mononuclear and dinuclear cobalt (II) complexes form from p[H] 2 through 11 in aqueous solution. The protonation constants of this ligand and stability constants of the 1:1, 1:2 ligand: cobalt(II) complexes were determined in KCl supporting electrolyte (μ = 0.100 M) at 25°C. The mechanism for the formation of dinuclear dioxygen cobalt(II) complexes is also described. The stability constants of mononuclear and dinuclear cobalt complexes were determined under nitrogen. Preliminary results show that the dinuclear dioxygen cobalt (II) complexes do not catalyze hydroxylation of adamantane in the presence of H₂S as two-electron reductant.     

The study on the effect and mechanism of the second ligands on the luminescence properties of terbium complexes

The binary complex of Tb(III) with N-phenylanthranilic acid (N-HPA) was synthesized, and the ternary complexes were synthesized by introducing 1,10-phenanthroline (Phen), 2,2'-dipyridyl (Bipy), trioctylphosphine oxide (TPPO) as the second ligand, respectively. These complexes were characterized by infrared spectra, UV spectra and fluorescence spectra. The effect and mechanism of different second ligands on the fluorescent intensity of the terbium N-phenylanthranilic acid complexes was discussed. It showed that all the complexes exhibited ligand-sensitized green emission. The luminescence intensity increased in the sequence of Tb(N-PA)(3)Phen相似文献   

Synthesis,characterization and in vitro biological activity of cobalt(II), copper(II) and zinc(II) Schiff base complexes derived from salicylaldehyde and D,L‐selenomethionine

New cobalt(II), copper(II) and zinc(II) complexes of Schiff base derived from D,L ‐selenomethionine and salicylaldehyde were synthesized and characterized by elemental analysis, IR, electronic spectra, conductance measurements, magnetic measurements and biological activity. The analytical data showed that the Schiff base ligand acts as tridentate towards divalent metal ions (cobalt, copper, zinc) via the azomethine‐N, carboxylate oxygen and phenolato oxygen by a stoichiometric reaction of M:L (1:1) to form metal complexes [ML(H₂O)], where L is the Schiff base ligand derived from D,L ‐selenomethionine and salicylaldehyde and M = Co(II), Cu(II) and Zn(II). ¹H NMR spectral data of the ligand and Zn(II) complex agree with proposed structures. The conductivity values between 12.87 and 15.63 S cm² mol^?1 in DMF imply the presence of non‐electrolyte species. Antibacterial and antifungal results indicate that the metal complexes are more active than the ligand. Copyright © 2010 John Wiley & Sons, Ltd.     

A new ternary Cu (II) complex with 4,7-dimethyl-1,10-phenanthroline and NOO-type tridentate Schiff base ligand: Synthesis,crystal structure,biomacromolecular interactions,and radical scavenging activities

NOO-type tridentate Schiff base, N-salicylidene-2-aminobenzoic acid, (H₂L), and its ternary Cu (II) complex containing H₂L Schiff base and 4,7-dimethyl-1,10-phenanthroline (4,7-dmphen), [Cu(4,7-dmphen)(H₂L)]₂7H₂O, have been synthesized and characterized by CHN analysis, ESI-MS, FTIR, and single-crystal X-ray diffraction techniques. The interaction of alone H₂L Schiff base ligand and ternary Cu (II) complex with biomacramolecules {calf thymus DNA (CT-DNA) and bovine serum albumin (BSA)} has been investigated by electronic absorption and fluorescence spectroscopy. The experimental results indicate that H₂L Schiff base ligand and ternary Cu (II) complex bind to CT-DNA by means of a moderate intercalation mode. Furthermore, the fluorescence quenching mechanism between H₂L Schiff base ligand and ternary Cu (II) complex with BSA possesses a static quenching process. Radical scavenging activity of H₂L Schiff base ligand and ternary Cu (II) complex was measured in terms of EC₅₀, using the DPPH and H₂O₂ methods. Biomacromolecule interactions and scavenging activity studies revealed that ternary Cu (II) complex yielded better results than H₂L Schiff base ligand alone.     

Ln(Ⅲ)与2-羟基-1-萘醛缩蛋氨酸盐及邻菲咯啉三元配合物的合成与表征

合成了稀土硝酸盐与希夫碱盐2-羟基-1-萘醛缩蛋氨酸钾(以KL表示)及邻菲咯啉(Phen)的四种固体三元配合物。通过元素分析，IR，UV，DTA-TG及摩尔电导分析等手段确定配合物的组成为[Ln(L)(Phen)(NO3)(H2O)]NO3(Ln＝Gd，Dy，Er，Yb)，并对它们的配合方式及某些物理和化学性质进行了研究。     

Mixed ligand five coordinate cobalt(II) complexes of a polymer-bound schiff base derived from 2-aminobenzimidazole

The complexes resulting from the interaction of a new Schiff base ligand derived from crosslinked polystyrene bound benzaldehyde and 2-aminobenzimidazole with a square planar complex [Co(TPP)] (where TPP = meso-tetraphenylporphyrin), and also with tetrahedral complexes [Co(BPBI)₂X₂] (where BPBI = 1-benzyl-2-phenylbenzimidazole, X = Cl, Br, or NCS) have been isolated and characterized. The percentages of cobalt and nitrogen in the complexes show that only one Schiff base unit is coordinated to cobalt. Infrared spectra suggest that the bonding of the polymer ligand to cobalt is through the N-3 atom of the benzimidazole moiety. The EPR spectra indicate that all the complexes are in the low-spin state and have a square pyramidal environment around cobalt(II). © 1992 John Wiley & Sons, Inc.     

Photoluminescence property of polymer–rare earth complexes containing acetaldehyde/aminophenol type bidentate Schiff base ligand

Acetaldehyde was introduced onto the side chains of polysulfone, and then Schiff base reactions were carried out between the introduced acetaldehyde and ortho-aminophenol (OAP) or meta-aminophenol (MAP). Two bidentate Schiff base (B) ligands of acetaldehyde/aminophenol type, OAPB and MAPB, were bonded on the side chains of polysulfone, and two new bidentate Schiff base ligand functionalized-polysulfones, PSF-OAPB and PSF-MAPB, were obtained. The triplet state energies of OAPB and MAPB are well matched with the resonant level energy of Tb(III), and the Tb(III) complexes emit the strong characteristic fluorescence of Tb(III) (green luminescence). Complexes of Eu(III) have no fluorescence emission because of the mismatching of the energy levels. In comparison, the fluorescence intensity of the binary complex PSF-(MAPB)₃-Tb(III) is stronger than that of the binary complex PSF-(OAPB)₃-Tb(III) because of the structured difference of the chelating ring. The ternary complexes PSF-(MAPB)₃-Tb(III)-(Phen)₁ (Phen represents 1,10-phenanthroline) and PSF-(OAPB)₃-Tb(III)-(Phen)₁ have stronger fluorescence emissions than the corresponding binary complexes. The fluorescence emission intensities of solid films of the complexes are stronger than that of their solutions. The prepared luminescent polymer-Tb(III) complexes containing acetaldehyde/aminophenol type bidentate Schiff base ligands have very high quantum yields (80–86%), reflecting the high intramolecular energy transfer efficiencies from the ligands to Tb(III).     

邻香草醛缩丙氨酸盐及邻菲咯啉与Ln(Ⅲ)三元配合物的合成与表征

某些水扬醛类氨基酸的金属配合物具有特殊的性质和应用[1 ,2 ] ,近年来 ,过渡金属离子的此类希夫碱配合物有不少报道。本工作在无水乙醇体系中 ,用稀土硝酸盐与邻香草醛缩丙氨酸钾及邻菲咯啉作用合成了未见文献报道的三种混配配合物 ,并对其组成和配位方式进行了研究。1　实验部分1 1　主要仪器与试剂美国Ｂｉｏ ＲａｄＦＩＳ1 65型红外光谱仪 ,ＫＢｒ压片 ;美国ＰＥ2 4 0 0 (Ⅱ )型元素分析仪 ;岛津ＵＶ 30 0 0双光束分光光度计 ;ＤＤＳ 1 1Ａ型电导率仪 ;德国ＳＴＡ40 9ＺＰ热分析仪。Ｌｎ2 Ｏ3纯度高于 99 9% ;ＤＬ α 丙氨酸为生化试剂…     

Ternary Complexes in Solution: Mixed Ligand Pb(II) Complexes with 2,2′-Bipyridyl or 1,10-Phenanthroline and Some Bivalent Mercapto Acid Amides

Abstract

The stability constants of ternary Pb(II) complexes containing 2,2′-bipyridyl (Bipy) or 1,10-phenanthroline (phen) as the first ligand and N-phenyl-2-mercapto acid amide, N-(p-chloro)phenyl-2-mercapto acid amide, N-(p-tolyl)-2-mercapto acid amide, N-(p-anisyl)-2-mercapto acid amide, or N-phenyl-2-mercapto-propionamide as the second ligand were determined in 70% v/v dioxane-water medium at 30 ± 1°C and constant ionic strength (0.1 M NaClO₄) in a nitrogen atmosphere. The results give evidence that all these complexes have the same structure and therefore the binding sites of the ligands have to be the imino nitrogen and sulfur of the sulfhydryl group. The stability difference between the ternary and the binary complexes are in good agreement with this interpretation. It is of interest to note that these ternary complexes are significantly more stable than expected from statistical reasons, i.e., the difference; Δ log K_M = log K^MA _MAL - log K^M _ML is positive (except for PMP) (where A = Bipy or phen and L is the second ligand). In addition, the enhanced stability of the ternary complexes is suggested on the basis of the π-accepting qualities of the hetero aromatic N-base. The effect of the chelate ring size is discussed.     

Eu(Ⅲ) complex-doped PMMA having fast radiation rate and high emission quantum efficiency

Three Eu(Ⅲ) ternary complexes,Eu(hfa-H) 3(Phen),Eu(hfa-H) 3(Bipy) and Eu(hfa-H) 3(Bath)(hfa = hexafluoroacetylacetonate,Phen = 1,10-phenanthroline,Bipy = 2,2 0-bipyridine,Bath = bathophenanthroline),were synthesized.Their luminescent properties were studied by incorporating deuterated Eu(Ⅲ) complexes in a poly(methylmethacrylate)(PMMA) matrix,and the results indicated that luminescent PMMA including Eu(hfa-D) 3(Bath) showed promising results for applications to novel organic Eu(Ⅲ) devices,such as the high-power laser materials.Additionally,all the three Eu(Ⅲ) complexes exhibited good thermostabilization.     

Novel hybrids of Cu2+ ternary complexes of salicylidene-amino acid Schiff base with phenanthroline（or bipyridine） intercalated in Mg/Al-NO3-layered double hydroxide

Four Cu²⁺ complexes of salicylidene-amino acid Schiff base with 1,10-phenanthroline（Phen） or 2,2’- bipyridine（Bipy） were successfully intercalated in interlayer galleries of Mg/Al-NO₃-layered double hydroxide（LDH） by the swelling-restored method.The hybrids were characterized by elemental analysis,X-ray diffraction,FT-IR spectra,UV-vis DRS,TG-DTA and SEM observation.Good protection of the complexes by LDH in neutral and weak acidic solutions was revealed by UV spectra,cyclic voltammograms and luminescence spectra.     

Syntheses,characterization and biological studies of zinc(II), copper(II) and cobalt(II) complexes with Schiff base ligand derived from 2‐hydroxy‐1‐naphthaldehyde and selenomethionine

Novel zinc(II), copper(II), and cobalt(II) complexes of the Schiff base derived from 2‐hydroxy‐1‐naphthaldehyde and D, L ‐selenomethionine were synthesized and characterized by elemental analysis, IR, electronic spectra, conductance measurements, magnetic measurements and powder XRD. The analytical data showed the composition of the metal complex to be ML(H₂O), where L is the Schiff base ligand and M = Co(II), Cu(II) and Zn(II). IR results confirmed the tridentate binding of the Schiff base ligand involving azomethine nitrogen, naphthol oxygen and carboxylato oxygen atoms. ¹H NMR spectral data of lithium salt of the Schiff base ligand [Li(HL)] and ZnL(H₂O) agreed with the proposed structures. The conductivity values of complexes between 12.50 and 15.45 S cm² mol^?1 in DMF suggested the presence of non‐electrolyte species. The powder XRD studies indicated that Co(II) complex is amorphous, whereas Cu(II) and Zn(II) complexes are crystalline. The results of antibacterial and antifungal screening studies indicated that Li(HL) and its metal complexes are active, but CuL(H₂O) is most active among them. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of nickel(II), cobalt(II), copper(II), manganese(II), zinc(II), zirconium(IV), dioxouranium(VI) and dioxomolybdenum(VI) complexes of a new Schiff base derived from salicylaldehyde and 5-methylpyrazole-3-carbohydrazide

Summary Synthesis of a new Schiff base derived from salicylaldehyde and 5-methylpyrazole-3-carbohydrazide, and its coordination compounds with nickel(II), cobalt(II), copper(II), manganese(II), zinc(II), zirconium(IV), dioxouranium(VI) and dioxomolybdenum(VI) are described. The ligand and the complexes have been characterized on the basis of analytical, conductance, molecular weight, i.r., electronic and n.m.r. spectra and magnetic susceptibility measurements. The stoichiometries of the complexes are represented as NiL · 3H₂O, CoL · 2H₂O, CuL, MnL · 2H₂O, ZnL · H₂O, Zr(OH)₂(LH)₂, Zr(OH)₂L · 2MeOH, UO₂L · MeOH and MoO₂L · MeOH (where LH₂ = Schiff base). The copper(II) complex shows a subnormal magnetic moment due to antiferromagnetic exchange interaction while the nickel(II), cobalt(II) and manganese (II) complexes show normal magnetic moments at room temperature. The i.r. and n.m.r. spectral studies show that the Schiff base behaves as a dibasic and tridentate ligand coordinating through the deprotonated phenolic.oxygen, enolic oxygen and azomethine nitrogen.     

基于柔性四羧酸及4,4'-联吡啶的sqc422型钴(Ⅱ)配位聚合物

采用水热法合成了一种基于1,3-二[3,5-(二羧基)苯氧基]-2-羟基丙烷(H4L)和4,4′-联吡啶(Bipy)的Co(Ⅱ)配合物:[Co2(L)(Bipy)2]n(1),并利用红外光谱(IR)、紫外-可见光谱(UV-Vis)、热重分析(TGA)、单晶X-射线衍射、粉末X射线衍射(XRD)及元素分析对其结构进行了表征。配合物1属单斜晶系,C2/c空间群。在配合物1中,由2个六配位钴原子组成的双核原子簇可简化为八面体型6-连接点,连接4个羧酸配体分子L和其他2个双核原子簇。羧酸配体L可简化为四面体型4-连接点,连接4个双核原子簇。平行排列的2个联吡啶分子连接两个相邻双核原子簇,相当于"双桥",简化为拓扑回路的边。因此,配合物1的骨架描述为sqc422拓扑网络。     

Synthesis of transition metal complexes containing a Schiff base ligand derived from 1,10-phenanthroline-2,9-dicarboxaldehyde and 2-aminobenzenethiol

The synthesis of a new Schiff base containing 1,10-phenanthroline-2,9-dicarboxaldehyde and 2-aminobenzenethiol subunits is described. The reaction of 1,10-phenanthroline-2,9-dicarboxaldehyde with 2-aminobenzenethiol leads to the isolation of 2,9-bis(2-benzothiazolinyl)-1,10-phenanthroline (I) which undergoes rearrangement when reacted with cobalt, nickel, copper or zinc ions to produce complexes of the tautomeric Schiff base 2,9-bis[2-(2-mercaptophenyl)-2-azaethene]-1,10-phenanthroline (L). The [Cu(L)ClO₄][ClO₄] and [M(L)X₂] complexes (where M = Co(II), Ni(II) and Zn(II) and X = Br) were characterized by physical and spectroscopic measurements which indicated that the ligand is acting probably as a tetradentate N₄ chelating agent.     

基于邻香草醛缩2-氨基-4-硝基苯酚的Schiff碱有机锡配合物的合成、晶体结构及生物活性

邻香草醛缩2-氨基4-硝基苯酚(H₂L)分别与二丁基氧化锡、二苄基二氯化锡反应, 合成了二丁基锡Schiff碱配合物(1)和单苄基Schiff碱配合物(2)。配合物经元素分析、¹H NMR、¹³C NMR、IR、UV-Vis表征, 并用X-射线单晶衍射测定了分子结构。研究了配体H₂L及配合物1、2对癌细胞Hela、MCF7、HepG2、Colo205、NCI-H460的抑制活性, 结果表明配合物1对这5种癌细胞的抑制效果优于现有抗癌药物卡铂, 可作为抗癌药物的候选化合物。在Tris缓冲溶液中, 以EB做为荧光探针, 用荧光光谱法研究了配体H₂L及配合物2与鲱鱼精DNA的相互作用, 结果表明配合物与DNA作用主要是由于Schiff碱配体协同效应所致。     

Complexes of iridium(I) with 2,2′-bipyridine and 1,10-phenanthroline: Synthesis and reactions of cationic complexes with diolefins

The synthesis and reactions of Ir^I complexes of the type [IrChel(L—L)]⁺ (Chel = Bipy or Phen; L—L = cyclooctadiene or 2,5-norbornadiene) are described. Coordinative- and oxidative-addition, and substitution reactions are compared with those of the corresponding Rh^I derivatives.     

基于邻香草醛缩2-氨基-4-硝基苯酚的Schiff碱有机锡配合物的合成、晶体结构及生物活性

邻香草醛缩2-氨基4-硝基苯酚(H₂L)分别与二丁基氧化锡、二苄基二氯化锡反应, 合成了二丁基锡Schiff碱配合物(1)和单苄基Schiff碱配合物(2)。配合物经元素分析、¹H NMR、¹³C NMR、IR、UV-Vis表征, 并用X-射线单晶衍射测定了分子结构。研究了配体H₂L及配合物1、2对癌细胞Hela、MCF7、HepG2、Colo205、NCI-H460的抑制活性, 结果表明配合物1对这5种癌细胞的抑制效果优于现有抗癌药物卡铂, 可作为抗癌药物的候选化合物。在Tris缓冲溶液中, 以EB做为荧光探针, 用荧光光谱法研究了配体H₂L及配合物2与鲱鱼精DNA的相互作用, 结果表明配合物与DNA作用主要是由于Schiff碱配体协同效应所致。