Condensed heteroaromatic systems including a thiophene ring.

The thermal stabilities of 2-mercapto-3-formylbenzo[b]thiophene and its chelates with Cu(II) and Co(II), of 2-mercapto-3-iminomethylbenzo[b]thiophene and its chelates with Cu(II), Co(II), Ni(II), and Zn(II), and of N,N′-bis(2-mercaptobenzo [b]-3-thenylidene)ethylenediamine and its chelates with Cu(II), Co(II), and Ni(II) were investigated by differential-thermal and thermogravimetric analysis. The temperature of the onset of decomposition and the character of the decomposirion of the ligands and chelates were established. It was found that the investigated chelates can be arranged in the following order with respect to increasing thermal stability: Cu < Co < Zn < Ni. The most thermally stable ligand is N,N-bis (2-mercaptobenzo[b]-3-thenylidene)ethylenediamine. The effectiveness of the ligands and chelates as stabilizers for polycaproamide fibers were compared. It was found that of the investigated compounds, the copper chelates are effective stabilizers. In a study of the thermal behavior of the copper chelates in an inert gas atmosphere it was established that the character of the thermal decomposition of the most effective of them — {it(N,N′-bis)2-mercaptobenzo[b]-3-thenylidene)-ethylenediaminato} Cu(II) — is identical both in the presence of air oxygen and in a nitrogen atmosphere, i.e., the chelate does not undergo oxidation at temperatures up to 270?C.     

Substituierte 2-Jodacetessigsäureanilide als Chelatbildner

A method of preparing various substituted 2-iodoacetoacetanilides is presented. The dissociation constants of these compounds and the stability constants of their copper chelates were determined by potentiometric pH-measurements. The influence of the substituents at the phenyl and also the chelate ring on the complexing behaviour of the 2-iodoacetoacetanilides is discussed.     

Struktur-Reaktivitäts-Beziehungen bei koordinativ ungesättigten Chelatkomplexen. III. Vergleich des Akzeptorverhaltens der Nickel- und Cobalt(II)-Chelate von dreizähnigen,dianionischen Schiffschen Basen

Structure Reactivity Relations of Coordinatively Unsaturated Chelate Complexes. III. Acceptor Tendency of Nickel and Cobalt Chelates with Tridentate Di-anionic Schiff Base Ligands The reactivity of nickel and cobalt chelate complexes of the type 3 with several donors is compared by isolation of stable adducts. In the case of nickel the reactivity is vigorously influenced by the substituents R¹ and R². The equatorial and the axial unoccupied coordination centers of the nickel chelates exhibit a markedly different behaviour. The cobalt(II) chelates – all of them are high spin complexes – favour O-donors. The complicate composition of the adducts point to a polynuclear structure. With pyridine, high spin diadducts have been isolated probably with coordination number 5 for the metal.     

Synthesis, spectroscopic characterization and ESR studies on electron transfer reactions of bis[N-(2,6-di-tert-butyl-1-hydroxyphenyl)salicylaldiminato]-copper(II) complexes with PbO2 and PPh3

New bis[N-(2,6-di-t-butyl-1-hydroxyphenyl)salicylideneminato]copper(II) complexes bearing HO and CH3O substituents on the salicyaldehyde moiety were prepared, and their spectroscopic properties, as well as redox reactivity towards PbO2 and PPh3, examined by ESR and UV spectroscopy. In the process of synthesis of HO complexes unlike CH3O the oxidative C-C coupling of coordinated salicylaldimine ligands does not takes place. The powder ESR spectra of CH3O substituted complexes unlike of HO analogues are typical of a triplet state Cu(II) dimers with a half-field forbidden (deltaM = +/- 2) transition and the allowed transitions (AM = +/- 1) dimeric form of the complexes at 300 and 113 K. The one-electron oxidation of 3-CH3O and all of the OH complexes with PbO2 to give indophenoxyl type secondary radicals which are significantly different from those observed for analogues Cl, Br and NO2 substituted chelates. The presented complexes unlike their electron-withdrawing analogues are readily reduced by PPh3 via intramolecular electron transfer from ligand to copper(II) to give various radical intermediates as well as Cu(I) radical ligand compounds. The analysis of ESR spectra all of the complexes and radical intermediates are presented.     

Studies on imidazole derivatives as chelating agents-IV Stability constants of the metal chelates of azoimidazoles

Chelating abilities of several azoimidazoles containing a hydroxy and/or a dimethylanuno group, and the structures of their copper chelates, were investigated. 1-(5-Methyl-4-imidazolylazo)-2-naphthol(IAN) formed a brown-black chelate having the composition Cu(ligand)Br whereas 4-(5-methyl-4-imidazolylazo)dimethylaminobenzene (DAI) formed a reddish brown chelate Cu(ligand)(2)Br(2).2H(2)O. The contribution of the phenolic OH and the imino NH group to the binding with copper is discussed from the infrared spectra. The metal : ligand ratios of the Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) chelates were determined by the method of continuous variations and their stability constants were determined at 25 degrees in 50% v v dioxane-water by the Bjerrum-Calvin method. The OH-containing azoimidazoles were found to form stable chelates with logK(1)K(2) values 14.9-25.4 and the stabilities approximately followed the Mellor-Maley stability sequence. The compound DAI, which has no OH group, formed weak chelates with Co(II), Ni(II) and Cu(II).     

Coordination compounds of transition metal hydrazine derivatives. Part 25. Monohydrazine-S-methylcarbodithioate schiff bases derived from α-dicarbonyl compounds

Summary The monohydrazones derived from the condensation of diacetyl and benzil with hydrazine-S-methylcarbodithioate (Dahydth) and (Benhydth) were prepared and their ligation properties with nickel(II), copper(II), palladium(II), zinc(II) and cadmium(II) were studied. A series of bisligand chelates were isolated and characterized. In the zinc(II), cadmium(II) copper(II) and palladium(II) bisligand chelates, both Dahydth and Benhydth act as mononegative bidentate molecules. The Ni(Dahydth-H)₂ chelate possesses an octahedral structure where Dahydth acts as a mononegative tridentate ligand. The¹H n.m.r. spectra of the two ligands as well as of the diamagnetic metal(II) chelates are discussed. The fragmentation in a mass spectrometer of all these chelates was also studied.     

Relationship between Coordination Structure and Biological Activity of Copper(II) Nicotinate

1 INTRODUCTION In 1945, Braude[1] found for the first time that adding copper (Cu) ten times the normal requisite amount into the feed can improve the production property of the animal obviously. Therefore, from then on copper has been widely applied in pig- breeding industry as an effective growth-promoting agent, especially in the process of intensive culture, which plays an important part in improving the growth of animal and the production property. However, at the same time, the high…     

Mono- and Binuclear Copper(II) Metal Chelates with 3,5-Di(tert-butyl)salicylaldehyde Acylhydrazones

Some new mono- and binuclear complexes of copper(II) acetate, nitrate, and perchlorate with acylhydrazones of substituted salicylaldehyde derivatives containing bulky tert-butyl substituents are synthesized. The structure and properties of the complexes isolated are shown to be determined by both the structural features of the ligand systems and by the nature of the acido ligands. The exchange parameters 2J ranging from –108 to –125 cm^–1 are calculated for the binuclear copper(II) metal chelates.     

Optically active cobalt(II) and copper(II) complexes with tetradentate Schiff bases derived from (N,N′)-(1R,2R)-(−)-cyclohexylenediamine and salicylaldehyde, 2-hydroxynaphthaldehyde or 2-hydroxyacetophenone

The Schiff bases obtained from (1R,2R)-1,2-cyclohexanediamine and salicylaldehyde, 2-hydroxynaphthaldehyde or 2-hydroxyacetophenone have been used as ligands for copper(II) and cobalt(II). The coordination compounds have been studied by u.v.–vis. absorption and by circular dichroism spectroscopy in solution. The complexes are four-coordinated in a slightly distorted square-planar geometry. The distortion from planarity is a main factor influencing the chiral surroundings of the metal ion. The d–d and c.t. transitions are consistent with the observed distortion which arises from intramolecular interactions between substituents at the Schiff base imine carbon and hydrogens of the cyclohexylene ring. Distortion is more pronounced in Co^II than in Cu^II complexes. In the Schiff base chelates the cyclohexane ring is trans-fused to the central chelate ring, forming a rigid structure in which the chelate ring is locked stereospecifically in the conformation.     

Chelate von β-Dicarbonylverbindungen und ihren Derivaten. XXIV. Stabilitätskonstanten von Metallchelaten unterschiedlich substituierter Pivaloylacylmethane

Chelates of β-dicarbonyl compounds and their derivatives. XXIV. Stability constants of metal chelates with differently substituted acylpivaloylmethanes Stoichiometric stability constants of copper(II), beryllium(II), nickel(II), cobalt(II) and zinc(II) chelates of 25 differently substituted acylpivaloylmethanes are determined in dioxane-water mixture and relations for calculating thermodynamic constants are given. The influence of aromatic and aliphatic substituents of the β-diketones on complex stability is discussed.     

铜(II)/明胶(酶解明胶)络合物的制备及其络合形态的探讨

许多金属元素对于生物体是必需的,Ｎａ、Ｋ、Ｍｇ、Ｃａ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｕ、Ｍｏ和Ｚｎ在人体中的含量约３％;各种金属离子在生物体中具有不同的作用,其功能是很复杂的．铜在生物体内主要是进行氧化还原反应,起输送氧气和电子载体的作用．如果人体内缺乏铜,则...     

Liquid–liquid extraction of copper(II) with substituted salicylideneanilines from sulfate media

The liquid–liquid extraction of copper(II) with Schiff bases in chloroform from sulfate media is studied for pH and concentration of the extractant. Stoichiometry coefficients of the extracted species are determined by the slope analysis method. With salicylideneaniline, the copper(II) is extracted as a mixed chelate complex, CuL₂HL. In the presence of substituent, the copper is extracted as simple chelates, CuL₂. The trends in the values of extraction constants were explained in terms of the nature of the substituents.     

Syntheses,Characterization and Anti-inflammatory Activity of a Benzamide Derivative and its Metal Chelates

N-Phenylbenzamide-2,2′-dicarboxylic acid (PBDA) and its copper(II), nickel(II), cobalt (II), zinc(II) and manganese(II) chelates have been synthesized and characterized by their physical measurements, infrared and electronic spectra and magnetic moment data. In an acute anti-inflammatory test, the cobalt chelate was most active (31.1% inhibition) followed by the zinc and copper chelates, whereas the copper chelate (22.3% inhibition) was most active in an adjuvant arthritis test. Again the cobalt chelate was most active in the cotton-wad granuloma test. Gastric irritancy was markedly reduced after chelation by copper, followed in order by zinc, cobalt, manganese and nickel chelates. © 1997 John Wiley & Sons, Ltd.     

A spectroscopic study of adducts of heterocyclic nitrogen bases with nickel(II) chelates of 2-methyl-5-nitrophenylthiocarbazone

A spectrophotometric method was employed to study the adduct formation constants of a few typical bases with nickel(II) chelates of 2-methyl-5-nitrophenylthiocarbazone. Monobasic bases such as pyridine and methyl-substituted pyridines form pentacoordinated adducts with a stoichiometry of 1:1 for metal chelate-base. The dibasic bases such as 1,10-phenanthroline, 2,2′-bipyridyl, etc. also exhibit 1:1 stoichiometry giving hexacoordinated adducts. The experimental results are discussed in terms of the basicity and steric factors of the various bases.     

Spectrophotometric Studies of Cobalt(II) and Copper(II) Chelates of 2-Picolylamine

Cobalt (II) and copper (II) chelates of 2-picolylamine have been studied spectrophotometrically in aqueous solution. Formation of 2-picolylamine chelates was pH dependent, and the optimum pH range of the cobalt (II) chelate was at pH 8.8-9.6, and copper(II) chelate at 4.7-6.8, respectively. The mole ratio of 2-picolylamine to both of metal(II) ions was found to be 2 to 1 stoichiometry. The spectrophotometric sensitivities are 0.23γ of Co/Cm² and 8.9γ of Cu/Cm³, at 373 mμ, pH 9.0 for Co(II) chelate and 588 mμ, pH 6.0 for Cu (II) chelate. The stability constants (logK) of the chelates CoL₂²⁺ and CuL₂²⁺ have been evaluated at a constant ionic strength of 0.10 at 20, 25, 30, 35 and 40°C. Enthalpy and entropy changes characterizing the formation of the chelates have been calculated at 25°C The results are collected as follows:      

Enantioselective oxidative biaryl coupling reactions catalyzed by 1,5-diazadecalin metal complexes: efficient formation of chiral functionalized BINOL derivatives

Chiral 1,5-diaza-cis-decalins have been examined as ligands in the enantioselective oxidative biaryl coupling of substituted 2-naphthol derivatives. Under the optimal conditions employing 2.5-10 mol % of a 1,5-diaza-cis-decalin copper(II) catalyst with oxygen as the oxidant, enantioselective couplings (44-96% ee) could be achieved for a range of 3-substituted 2-naphthols including the ester, ketone, phosphonyl, and sulfonyl derivatives. The relationship between the substitution of the naphthalene starting materials and reactivity/selectivity is determined by several factors which act in concert: (1) the effect of substituents on the oxidation potential of the substrate, (2) the ability of the substrate to participate in a chelated copper complex which depends on (a) the inherent coordinating ability of the 3-substituent and (b) substituent steric interactions that affect chelation between the 2-hydroxyl and 3-substituent, (3) the effect of substituents on dissociation of the product from the copper catalyst.     

Catalysis of copper(II) chelate-amine complexes in the oxidative coupling of 2,6-dialkylphenols

The oxidative coupling reaction of 2,6-dimethylphenol and 2,6-di-tert-butylphenol with molecular oxygen was performed by using a series of copper(II) chelate complexes as a catalyst, derived from copper(II), β-diketone, and some Shiff bases. Under the applied reaction conditions, the reaction products of 2,6-dimethylphenol were poly(2,6-dimethyl-1,4-phenylene oxide) (C? O coupling product) and 3,3′,5-5′-tetramethyl-4,4′-diphenoquinone (C? C coupling product), and that of 2,6-di-tert-butylphenol oxidation was only 3,3′,5-5′-tetra-tert-butyl-4,4′-diphenoquinone (C? C coupling product). The catalytic activity has been shown to be dependent on the properties of the copper(II) chelates used as catalysts and the mole ratios of amine ligand to copper(II) chelate (ligand ratio). The basicity and the steric bulkiness of the amine used as a ligand for copper(II) β-diketonato catalysts were found to be two of the main factors that govern the oxidative coupling mode (C? O and/or C? C coupling) of 2,6-dimethylphenol. The oxidative coupling activity of 2,6-dialkylphenol is discussed in terms of both the stabilities of the copper(II) chelates and of the copper(II) chelate-amine adducts. The rate of oxygen absorption for 2,6-dimethylphenol catalyzed by the copper(II) acetylacetonato-piperidine system is first order in oxygen partial pressure and zero order in 2,6-dimethylphenol concentration, respectively. A Cu(II)-oxygen, as an intermediate is suggested on the basis of the results obtained.     

Coordination compounds of hydrazine derivatives with transition metals. Part 21. Reaction of 1,5-thiocarbodihydrazones with nickel(II) and copper(II) salts

Summary A series of 1,5-thiocarhodihydrazones (HL) were reacted with nickel(II) acetate to give neutral bisligand nickel(II) chelates, Ni(L)₂. Reaction of nickel(H) chloride, however. results in partial hydrolysis of the dihydrazones to give Ni(RCH=NNHCSNHNH₂)₂Cl₂ chelate complexes. Deprotonation of these chelates with pyridine gave the neutral chelates Ni(RCH=NN=CSNHNH₂)₂. Copper(H) salts are readily reduced by the dihydrazone ligands to copper(I) chelates of the type CuL, Cu(HL)₂CI and Cu₂(HL)₃CI₂.     

Uranyl binary and ternary chelates of tenoxicam Synthesis, spectroscopic and thermal characterization of ternary chelates of tenoxicam and alanine with transition metals

Ternary Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and UO(2)(II) chelates with tenoxicam (Ten) drug (H(2)L(1)) and dl-alanine (Ala) (HL(2)) and also the binary UO(2)(II) chelate with Ten were studied. The structures of the chelates were elucidated using elemental, molar conductance, magnetic moment, IR, diffused reflectance and thermal analyses. UO(2)(II) binary chelate was isolated in 1:2 ratio with the formula [UO(2)(H(2)L)(2)](NO(3))(2). The ternary chelates were isolated in 1:1:1 (M:H(2)L(1):L(2)) ratios and have the general formulae [M(H(2)L(1))(L(2))(Cl)(n)(H(2)O)(m)].yH(2)O (M=Fe(III) (n=2, m=0, y=2), Co(II) (n=1, m=1, y=2) and Ni(II) (n=1, m=1, y=3)); [M(H(2)L(1))(L(2))](X)(z).yH(2)O (M=Cu(II) (X=AcO, z=1, y=0), Zn(II) (X=AcO, z=1, y=3) and UO(2)(II) (X=NO(3), z=1, y=2)). IR spectra reveal that Ten behaves as a neutral bidentate ligand coordinated to the metal ions via the pyridine-N and carbonyl-O groups, while Ala behaves as a uninegatively bidentate ligand coordinated to the metal ions via the deprotonated carboxylate-O and amino-N. The magnetic and reflectance spectral data confirm that all the chelates have octahedral geometry except Cu(II) and Zn(II) chelates have tetrahedral structures. Thermal decomposition of the chelates was discussed in relation to structure and different thermodynamic parameters of the decomposition stages were evaluated.     

肼基硫代甲酸酯配合物的合成、晶体结构、光谱及三阶非线性光 学性质研究

报道三种有推拉电子基团的肼基硫代酸酯衍生物配体(HL^1^～^3)。此类配体与二价过渡金属离子配位时脱去一质子,形成D-M-D和A-M-A(D=给体,M=金属,A=受体)类型、含有共轭体系的中性配合物。本文集中研究了该类配体的镍、铜、钯、铂配合物的IR、磁化率、ESR谱,电子光谱和三阶非线性光学性质,通过光谱研究初步确定了它们均为平面正方形构型配合物,文中还报道了CuL2^1的晶体结构。晶体属P1空间群,a=0.7835(2),b=1.0530(2),c=1.1816(2)nm,α=100.61(3),β=92.38(3),γ=110.00(3)ⅲ,Z=1,最终的R因子为0.063。通过晶体结构测试,进一步确定铜配合物的结构为平面构型。