Syntheses of homopolymer and water-soluble polymers containing tetraphenylporphinatomanganese(III) complex,and ligand substitution reaction for anionic ligand

A vinyl monomer containing the pendant tetraphenylporphyrin (TPP) group, 4-vinyltetraphenylporphyrin (VTPP), was synthesized. A homopolymer (PVTPP) which is insoluble in water, and three water-soluble polymers were obtained by radical polymerization. The water-soluble polymers are two anionic polymers (PVPTSPP and PVTPP-StSO₃) and a cationic polymer (PVTPP-VPyM). PVPTSPP has sulfonic acid groups in a TPP group and very high charge density. PVTPP-StSO₃ was obtained by copolymerization of VTPP and sodium 4-styrenesulfonate. PVTPP-VPyM was obtained by quarternarization of a copolymer of VTPP and 4-vinylpyridine. Polymeric manganese(III) complexes (PMn-VTPP, PMnVPTSPP, PMnVTPP-StSO₃, and PMnVTPP-VPyM) were prepared from the polymers and manganese acetate. The acetate ligand in PMnVTPP can be easily substituted by another ligand such as Cl^?, AcO^?, OH^?, and SCN^?. The substitution reaction occurs in the interface between water and chloroform. The sulfonated homopolymer, PMnVPTSPP, cannot incorporate with anionic ligands because of the strong electrostatic repulsion. In the anionic copolymer, PMnVTPP-StSO₃, the ligand substitution reaction with SCN ligand needs activation energy of 53 kJ/mol. In the cationic polymer complex, PMnVTPP-VPyM, the OH ligand can be easily substituted with the SCN ligand and the equilibrium constant of the reaction was estimated at 1.38 × 10^?3. © 1994 John Wiley & Sons, Inc.     

Intramolecular Antiferromagnetism in μ-Oxo-bis[(5,15-dimethyl-2,3,7,8,12,13,17,18-octaethylporphyrinato)iron(III)]

The magnetism of μ-oxo-bis[(5,15-dimethyl-2,3,7,8,12,13,17,18-octaethylporphyrinato)iron(III)] with bridge geometry d(Fe? O) = 1.752 Å and ?(Fe? O? Fe) = 178.6° can be explained in terms of antiferromagnetically exchange coupled iron(III)-3d⁵ pairs. The magnetochemical analysis in the temperature range 6K–295K on the basis of the isotropic Heisenberg model (spin Hamiltonian: ? = ?2J?₁ · ?₂ S₁ = S₂ = 5/2) leads to the exchange parameter J = ?125 cm^?1. With regard to the Fe? O bond length the J value corresponds to the series of data observed for other μ-oxodiiron-porphyrins and -porphycenes. Compared to the spin-spin coupling in [Fe₂Cl₆O]^2?, |J| is enhanced by ≈ 10%.     

Synthesis and magnetic properties of copper (II)-lanthanoid (III) binuclear complexes with N,N′-bis(3-aminopropyl) oxamido ligand

Six novel μ-oxamido binuclear complexes, namely Cu(axpn)Ln(L)₂(ClO₄)₃ (Ln: Eu, Gd, Tb, Nd, Ho, Er), where oxpn is N,N'-bis(3-aminopropyl) oxamido, L denotes 5-nitro,10-phenanthroline (abbreviated as NO₂-phen), have been synthesized and characterised. The magnetic susceptibility of complexes Cu(oxpn)Gd(NO₂-phen)2(ClO₄)₃.2H₂O was measured over the 4–300 K and the observed data were successfully simulated by equation based on spin Hamiltonian operator (H = -2J₁ · S₂), giving the exchange integral J(Cu-Gd)=-1.62 cm^?1. This indicates a weak antiferromagnetic interaction between the Cu(II) and Gd(III) ions.     

Thallium-205 NMR spectroscopy. Solvation of the Tl(l) ion in the binary solvent systems water/pyridine,water/dimethyl sulfoxide,and pyridine/dimethyl sulfoxide

Solvation of the Tl⁺ ion in 0.005M solutions of water/pyridine, water/dimethyl sulfoxide, and pyridine/dimethyl sulfoxide was studied with ²⁰⁵ Tl NMR spectroscopy as a function of solvent composition and anion (NO ₃ ^– and ClO ₄ ^t- ). Dimethyl sulfoxide solvated the Tl⁺ ion more strongly than did pyridine, despite the latter's greater electron-donating ability. This was explained in terms of structural effects, which were found to be large for all three binary solvent systems. Ion pairing was evident in the DMSO/pyridine and water/pyridine solvent systems in which the pyridine mole fraction was greater than 0.8.     

Resonance Raman spectra of tris(acetylacetonato)iron(III) and ruthenium(III) complexes and their solvent effect

The resonance Raman spectra of tris(acetylacetonatoiron(III)) and ruthenium(III) complexes in various solvents and in water-acetonitrile (W-AN) mixtures were measured. The resonance Raman spectra of both complexes indicated peaks near 460 and around 1580 cm^–1. Thev(C-O) peak (around 1580 cm^–1) is shifted to low frequency with an increase in the dielectric constant _T of the solvents, whereas thev(M-O) (M=Fe and Ru, near 460 cm^–1) are constant, independent of _T. It implies that the C-O bond in the acac^– ligand is lengthened by the polarizability effect of the solvents, while both the Fe-O and Ru-O bonds, which are located in the inside of the complexes, are not influenced by the solvents indicating that the interaction does not depend on the properties of individual solvent molecules but on those of the aggregate.     

Oxidovanadium (IV) and iron (III) complexes with O2N2 donor linkage as plausible antidiabetic candidates: Synthesis,structural characterizations,glucose uptake and model biological media studies

With the upsurging cases of type II diabetic patients, the demand for safe and effective oral antidiabetic drugs is also increasing. Coordination complexes have proven their mettle as efficient oral drug candidates, which thereby motivated us in this work to design new transition metal complexes as plausible candidates for the treatment of diabetes. A reduced salen ligand, {H₂(hpdbal)₂-an} ( 1 ) derived vanadium (IV) and iron (III) complexes, namely, [V^IVO{(hpdbal)₂-an}] ( 2 ) and [{Fe^III (OH₂)((hpdbal)₂-an)}₂ μ₂-SO₄] ( 3 ) were synthesized in this study. The newly obtained ligand and complexes were characterized using usual analytical and spectroscopic techniques. The potential of these compounds in inducing increased glucose uptake by diabetic cells were studied by using insulin resistant HepG2 cells as model diabetic cells and 2-NBDG molecule as a D-glucose analogue and fluorescent tracker. The cells added with the vanadium (IV) complex 3 induced significant NBDG uptake of 95.4% which was higher than that induced by metformin, the standard antidiabetic drug. To elucidate the behavior of the complexes in biological media, model solution studies were conducted with a wide range of pH conditions and protein bovine serum albumin (BSA). The complexes demonstrated effective binding with BSA which was concluded through spectroscopic titration studies and were also found to be sufficiently stable over physiological pH conditions. The study can thus prove to be beneficial in the quest for new antidiabetic drugs.     

两个双核铁（Ⅲ）和三足配体的配合物的合成和晶体结构

运用三足四齿配体三（2－甲基吡啶）胺（TPA）或三（2－甲基苯丙咪唑）胺（TBA）,得到两个双核铁(III)配合物，[Fe₂L₂(μ₂-O)(μ₂-p-NH₂-C₆H₄COO)]³⁺ (L = TPA, 1 和 L = TBA, 2)。两个配合物均为单斜晶系，空间群为P2(1)/c.晶胞参数 1: a = 1.4529(4), b = 1.6622(5), c = 2.0625(6) nm, β= 100.327(5)º, V = 4.900(3) nm³, z = 4, F(000) = 2344, 分子量M_r = 1142.91, Dc = 1.549 g/cm³, R₁ = 0.0544, R₂ = 0.0962. 2: a = 1.3378(4), b = 2.1174(7), c = 2.4351(7) nm, β= 97.315(6)º, V = 6.842(4) nm³, z = 4, F (000) = 3116, 分子量M_r = 1505.08, Dc = 1.444 g/cm³, R₁ = 0.0793, R₂ = 0.1623. 在两个双核铁(III)配合物中，中心的三价铁和配体TPA或TBA上的四个氮原子和两个氧原子通过不同的桥形成一个畸变的八面体构型。     

Synthesis,structures, and characterization of copper(II), nickel(II), and cobalt(III) metal complexes derived from an asymmetric bidentate Schiff-base ligand

An asymmetric bidentate Schiff-base ligand (2-hydroxybenzyl-2-furylmethyl)imine (L–OH) was prepared. Three complexes derived from L–OH were synthesized by treating an ethanolic solution of the appropriate ligand with an equimolar amount of metallic salt. Three complexes, Cu₂(L–O^?)₂Cl₂ (1), Ni(L–O^?)₂ (2) and Co(L–O^?)₃ (3), have been structurally characterized through elemental analysis, IR, UV spectra and thermogravimetric analysis. Single crystal X-ray diffraction shows metal ions and ligands reacted with different proportions 1?:?1, 1?:?2 and 1?:?3, respectively, so copper(II), nickel(II), and cobalt(III) have different geometries.     

Intradiffusion and viscosity measurements in acidified iron(III) chloride solutions at 25°C

Intradiffusion of species in acidified (using eithe hydrochloric or perchloric acid) iron(III) chloride solutions has been studied using labeled iron(III), chloride and water. Comparison with data for iron(III) perchlorate has enabled the influence of complexed species upon the diffusion to be ascertained. The chloro-iron species formed have larger diffusion coefficients than the free iron(III) ion as would be expected from their lower net charge. Simple diffusion models have been employed to enable estimates of the diffusion of the complexed species and of the free chloride diffusion coefficients to be obtained. These are discussed in relation to literature data for similar systems. In addition esitmates of the effective hydration of the iron(III) species in solutions have been obtained from the diffusion data. These are discussed in relation to two other trivalent metal salt systems, chromium chloride and lanthanum chloride; the overall hydration of the three cations is virtually identical.     

Structure of iron (II) and cobalt (II) bromide complexes in aqueous solution by X-ray diffraction analysis

Structures of bromo-metal complexes in concentrated aqueous solutions of FeBr₂ and of CoBr₂ were investigated by X-ray diffraction analysis. The complexes possess an octahedral geometry coordinating Br^– along with H₂O ligands. The frequency factors of metal-Br contacts per one atom of metal were 0.325 for the 2.7M (mol-dm^–3) and 0.747 for the 4.5M FeBr₂ solutions, and 0.280 for the 2.8M and 0.595 for the 4.3M CoBr₂ solutions. The frequency factors suggested that the tendency of metal ions to forming monobromo complexes is in the order, Fe>Co>Ni相似文献   

Synthesis,structures and properties of cobalt(III) and iron(III) complexes with a new triazamacrocycle, 1,4-diacetate-1,4,7-triazacyclodecane

A new bidisplaced acetate functionalized pendant arm derivative, 1,4-diacetate-1,4,7-triazacyclodecane (L) and its corresponding Co(III), Fe(III) complexes [CoLCl] (1) and [FeLCl]₂ · 3H₂O (2) were synthesized and characterized by elemental analysis, IR spectra,UV–Vis spectra, HNMR, MS, XPRD, TGA and single-crystal X-ray diffraction analysis. The crystal structure shows the metal ions in the complexes have similar coordination six-coordinate, by three nitrogens and two oxygens of the chelate ligand, and a chloride. Through calculation of the twist angle, we discover 1 forms a distorted octahedral geometry while 2 forms a distorted-prismatic geometry. In 2, there are abundant hydrogen bonds between the oxygen atoms of water and the nitrogens and oxygens of the ligand, resulting in a two-dimensional supramolecular network with a regular triatomic water cluster. The thermal gravimetric analyses of the two complexes are also given.     

Preparation,crystal structure,and infrared characterization of the first thiocyanato-oxy-antimonate(III) [(CH3)4N]2[Sb6O4(NCS)12]

The salt [(CH₃)₄N]₂[Sb₆O₄(NCS)₁₂] is the first identified thiocyanato-oxy-antimonate(III) complex. Reported are details of the synthesis, relevant infrared data and its x-ray structure. The compound crystallizes in the triclinic space group P1 with Z = 2 (C₁₀H₁₂N₇O₂S₆Sb₃) and unit cell dimensions a = 11.314(6), b = 12.846(3), c = 8.679(2) Å; α = 91.93(3)°, β = 90.31(3)° and γ = 99.13(3)°. It contains centrosymmetric [Sb₆O₄(NCS)₁₂]^2? anions packed with isolated tetramethyl-ammonium cations. The fundamental structural element of the anion is provided by the fusion of three SbOSbO rings forming a zig-zag portion of a ribbon, only slightly pleated. Peculiar is the unequivalence of the six thiocyanate ligands, though all primarily N-bonded to antimony atoms. Three thiocyanates are terminal while other three are asymmetrically N-bridging between two centers; two of this latter type are also interconnecting the anions via Sb???S contacts. There are three different antimony environments, the primary bonding at Sb being to one nitrogen and three oxygens, to one oxygen and three nitrogens and to two atoms of each type.     

Singlet quenching of tetraphenylporphyrin and its metal derivatives by iron(III) coordination compounds

The quenching of fluorescence of the free-base tetraphenylporphyrin, H₂TPP, and its metal derivatives, MgTPP and ZnTPP by diverse iron(III) complexes, [Fe(CN)₆]³⁻, Fe(acac)₃, [Fe(mnt)₂]⁻, Fe(Salen)Cl, [Fe₄S₄(SPh)₄]²⁻·, FeTPPCl and [Fe(Cp)₂]⁺ has been studied both in homogeneous medium (CH₃CN) and micellar media, SDS., CTAB and Triton X-100. The quenching efficiencies are analysed in terms of diffusional encounters and it has been possible to separate static quenching components. The quenching constants are dependent on the nature of the ligating atoms around iron(III) and also on the extent of π-conjugation of the ligands. The quenching mechanism has been investigated using steady-state irradiation experiments. Evidence for oxidative quenching by iron(III) complexes was obtained, though the spin multiplicities of the excited electronic states of iron(III) complexes permit both energy and electron transfer mechanisms for quenching of the singlet excited state of the porphyrins.     

Kinetics and mechanism of oxidation of glycine by iron(iii)-1,10-phenanthroline complex in perchloric acid medium

Kinetics and mechanism of oxidation of glycine by iron (III)-1,10-phenanthroline complex has been studied in perchloric acid medium. The reaction is first order with respect to iron(III) and glycine. An increase in (phenanthroline) increases the rate, while increase in [H⁺] decreases the rate. Hence it can be inferred that the reactive species of the substrate is the zwitterionic form and that of the oxidant is [Fe(phen)₂(H₂O)₂]³⁺. The proposed mechanism leads to the rate law as elucidated.     

Redox kinetics of metal complexes in nonaqueous solutions: Oxidation of a series of tris(1,10-phenanthroline)iron(II) ions by hexakis(trimethylphosphate)iron(III) in acetonitrile — A reactivity-selectivity relationship

Summary The kinetics of outer-sphere oxidation of Fe(Xphen) ₃ ²⁺ ions (X=H or several methyl substituents) in acetonitrile (MeCN) solution by iron(III), introduced as Fe(tmp)₆(ClO₄)₃ (tmp=trimethylphosphate), have been investigated at 25°C. The reactions are very complex because of solvation equilibria betweentmp andMeCN coordinated at Fe³⁺, with a reduction potential difference of 0.20 V for the replacement of onetmp byMeCN. This makes the various solvate species highly different in driving force. The second essential feature is the high charge-type of +2/+3. This brings about strong acceleration by salt because of ion association reducing the work necessary to overcome the Coulombic repulsion in forming the precursor complex.The task was to deconvolute two kinds of speciation: the ionic and the solvate speciations. The analysis suggests the concurrent existence of five Fe(tmp) _n ³⁺ (n=2–6) species among which four species (n=2–5) are reacting, with an additional mono and bis perchlorate ion pair for eachn. Extra complications arise as some of the solvation equilibria are not always fast compared to the redox reactions, leading to non-first order rate constants.Although the rate constants could not be defined with the desired precision, at least two results are worth noting: (i) The relative effects of driving force and charge are highlighted in controlling overall reactivity. (ii) The stronger the reducing power of the Fe(Xphen) ₃ ²⁺ moiety, the less it can distinguish between the various solvate species (reactivity-selectivity relationship).

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Redox-Kinetik von Metallkomplexe in nicht-wäßrigen Lösungsmitteln: Oxidation einer Serie von Tris(1,10-phenanthrolin)eisen(II)-Ionen mit Hexakis(trimethylphosphat)eisen(III) in Acetonitril-eine Reaktivitäts-Selektivitäts-Beziehung

Zusammenfassung Es wurde die Kinetik der Outer-sphere Oxidation einer Reihe von Fe(Xphen) ₃ ²⁺ Ionen (X=H oder verschiedene Methylsubstituenten) mit Eisen(III), eingeführt als Fe(tmp)₆(ClO₄)₃ (tmp=Trimethylphosphat), bei 25°C in Acetonitril (MeCN) untersucht. Diese Reaktionen sind sehr komplex, da gebundenestmp teilweise durchMeCN ausgetauscht wird, wobei der Ersatz einestmp-Moleküls durchMeCN das Redoxpotential um 0.2 V verschiebt. Deshalb sind die verschiedenen Solvatkomplexe in ihrer Reaktivität sehr unterschiedlich. Ein zweites wesentliches Merkmal der untersuchten Reaktionen ist der hohe Ladungstyp von +2/+3. Das bringt eine starke Erhöhung der Reaktionsgeschwindigkeit durch Elektrolytzusatz infolge von Ionenassoziation mit sich, die die Coulombsche Arbeit für die Bildung des Precursorkomplexes reduziert. Die Aufgabe bestand demnach in der Aufklärung von zwei Speziationsarten, der Solvations- und Ionenassoziationsgleichgewichte. Die Analyse weist auf das gleichzeitige Vorliegen von fünf Fe(tmp) _n ³⁺ Species (n=2–6) hin, wobei vier von ihnen (n=2–5) reagieren. Zusätzlich gibt es für jedesn noch Ionenpaare und Ionentriplets mit Perchlorat. Eine zusätzliche Komplizierung ergibt sich, weil bestimmte Solvationsgleichgewichte nicht immer schnell sind im Vergleich zu den Redoxreaktionen, die dann nicht mehr pseudo-erster-Ordnung sind.Wenn auch die Geschwindigkeitskonstanten nicht mit der üblicherweise gewünschten Präzision angegeben werden können, sind zumindest zwei Ergebnisse nennenswert: (a) Es wird die relative Bedeutung der driving force und der Reaktantenladung für die Gesamtreaktivität hervorgehoben und (b) Je stärker die Reduktionskraft des Fe(Xphen) ₃ ²⁺ Ions, desto weniger kann es die verschiedenen Solvatspezies unterscheiden (Reaktivitäts-Selektivitäts-Beziehung).

     

Speciation of iron (II) and (III) by using solvent extraction and flame atomic absorption spectrometry

A method for speciation, preconcentration and separation of Fe²⁺ and Fe³⁺ in different matrices was developed using solvent extraction and flame atomic absorption spectrometry. PAN as complexing reagent for Fe²⁺ and chloroform as organic solvent were used. The complex of Fe²⁺-PAN was extracted into chloroform phase in the pH range of 0.75-4.0 and Fe³⁺ remains in water phase in the pH range 0.75-1.25. The optimum conditions for maximum recovery of Fe²⁺ and minimum recovery of Fe³⁺ were determined as pH = 1, the stirring time of 20 min, the PAN amount of 0.5 mg and chloroform volume of 8 mL. The developed method was applied to the determination of Fe²⁺ and Fe³⁺ in tea infusion, fruit juice, cola and pekmez. It is seen that there is high bioavailable iron (Fe²⁺) in pekmez. The developed method is sensitive, simple and need the shorter time in comparison with other similar studies.     

Synthesis, reaction and structure of a series of chromium(III) complexes containing oxalate ligand

A series of chromium(III) complexes [Cr(bipy)(HC₂O₄)₂]Cl·3H₂O (1), [Cr(phen)(HC₂O₄)₂]Cl·3H₂O (2), [Cr(phen)₂(C₂O₄)]ClO₄ (3), [Cr₂(bipy)₄(C₂O₄)](SO₄)·(bipy)_0.5·H₂O (4) and [Mn(phen)₂(H₂O)₂]₂[Cr(phen)(C₂O₄)₂]₃ClO₄·14H₂O (5) were synthesized (bipy=4,4′-bipyridine, phen=1,10-phenanthroline), while the crystal structures of 1 and 3–5 have been determined by X-ray analysis. 1 and 3 are mononuclear complexes, 4 contains binuclear chromium(III) ions and 5 is a 3D supromolecule formed by complicated hydrogen bonding. 1–3 are potential molecular bricks of chromium(III) building blocks for synthesis heterometallic complexes. When we use these molecular bricks as ligands to react with other metal salts, unexpected complexes 4 and 5 are isolated in water solution. The synthesis conditions and reaction results are also discussed.