Multinuclear macromolecule metal complexes 2. Preparation and characterization of Prussian blue and its analogs bonded to pofy(vinylamine hydrochloride)

Prussian blue and its analogs bonded to poly(vinylamine hydrochloride) (PVAm · HCl) containing Fe^II or Fe^III and M²⁺ (M=Fe, Co, Cu) in a 11 molar ratio were obtained by the reaction of [Fe(CN)₆] ^n– (n=3,4) with M²⁺ ion-PVAm · HCl mixture in aqueous solution. Under a limited polymer concentration (T_VAm/T_Fe over 10), these polymer complexes thus obtained were stable and soluble in water. By casting these solutions, colored films can be produced. The formation of Prussian blue and its analogs bonded to PVAm · HCl was also investigated by the Benesi-Hildebrand method. The molar extinction coefficients of intervalence charge transfer (Fe^IIFe^III, Co^IIFe^III, Fe^IICu^II) band for MFe(CN)₆]^(n–2)– bound to PVAm · HCl (M=Fe, Co, Cu) were found to be 10,100–9601 · mol^–1 · cm^–1 at 25 C. The formation constants were found to be in the range of 10⁷ to 10¹⁰ M^–1. The changes of enthalpy (H) and entropy (S) were found to be in the range of –10.4 to –22.5 kJ · mol^–1 and 5.7 to 52.9 J · K^–1 mol^–1 respectively, at 25C.     

Magnetic anisotropy of cyclopropane and epoxide rings

MO LCAO results are presented for the interatomic contribution to the anisotropy of the diamagnetic susceptibility; values of _d=–23.5 · 10^–6 and _d=–13.8 · 10^–6 cm³/mole are obtained for the cyclopropane and epoxide ring systems, respectively. The results are used to interpret PMR spectra in terms of the configuration and conformation of the and forms of caran-4-ol and two stereoisomers of caranone.     

Heat capacity of indium from 300 to 1000 K

The heat capacity of high-purity indium has been determined by adiabatic-shield calorimetry in the range 300 to 1000 K. Values of thermodynamic functions have been calculated andC _p (1000 K), [H° (1000 K)–H° (298.15 K)], and [S° (1000 K)–S° (298.15 K)] are (27.11±0.15) J K^–1 mole^–1, (22873±70) J mole^–1, and (41.567 ±0.125) J K^–1 mole^–1, respectively. The enthalpy of fusion is (3283±7) J mole^–1 and the melting temperature (429.77±0.01) K. The premelting heat capacity is compatible with the presence of a mole fractionx 1·10^–6 of a liquid-soluble/solidinsoluble impurity in the sample.

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Zusammenfassung Die Wärmekapazität von hochreinem Indium wurde im Bereich von 300 bis 1000 K durch adiabatische Schildkalorimetrie bestimmt. Die Berechnungen der thermodynamischen Funktionen:C _p (1000 K), [H° (1000 K)–H° (298.15 K)] und [S° (1000 K–S° (298.15 K)] ergab 27.11±0.15 J K^–1 Mol^–1, (22 875±70) J Mol^–1, bzw. (41.567±0.125) J K^–1 Mol^–1. Die Schmelzenthalpie beträgt (3283±7) J Mol^–1 und die Schmelztemperatur (429.77±0.01) K. Die Vorschmelz-Wärmekapazität ist mit der Gegenwart einer Molfraktionx1×10^–6 einer flüssig-löslich/fest-unlöslichen Verunreinigung in der Probe vereinbar.

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Résumé La chaleur spécifique de l'indium de haute pureté a été déterminée entre 300 et 1000 K par calorimétrie adiabatique. Les valeurs des fonctions thermodynamiques suivantes ont été calculées:C _p (1000 K)=(27.11±0.15) J K^–1mol^–1, [H° (1000 K)–H° (298.15 K)]= (22 875±70) J mol^–1 et [S° (1000 K)–S° (298.15 K)]=(41.567±0.125) J K^–1 mol^–1. L'enthalpie de fusion est (3283±7) J mol^–1 et la température de fusion (429.77±0.01) K. La chaleur spécifique de pré-fusion est compatible avec la présence d'une fraction molairex1×10^–6 d'une impureté dans l'échantillon, soluble dans le liquide, insoluble dans le solide.

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C - 300 1000 . : _p(1000 ), [ (1000 ) — H (298,15 )] [S (1000 ) — S (298.15 )], : 27.11±0.15 . ^–1. ^–1, 2 2875±70 . ^–1 41.567±0.125 . ^{– 1–1}. 3283±7 .^–1, – 429.77±0,01 . - / 1.10^–6.

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The assistance of Bjørn Lyng Nielsen with the experimental work is recognized with thanks.     

Analytical applications of mixed-ligand complexes

Summary In medium of pH=1, vanadium(V) forms a 1 1 cationic complex with PAR, the instability constant of the complex beingpK=5.6. In the presence of hydrogen peroxide a 111 mixed-complex develops which is uncharged. The molar absorptivity of the complex ( ₅₄₀=1.28×10⁴ l·mole^–1·cm^–1) provides a possibility for the spectrophotometric determination of 1–65M hydrogen peroxide.

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Zusammenfassung In saurer Lösung (pH=1) bildet Vanadin(V) mit PAR einen positiv geladenen Komplex, dessen Komplexkonstante dem pK-Wert 5,6 entspricht. In Anwesenheit von Wasserstoffperoxid bildet sich mit diesem Kation ein ungeladener Mischkomplex im Verhältnis 111. Dessen Extinktionskoef-fizient ( ₅₄₀=1,28×10⁴ l · mol^–1 · cm^–1) ermöglicht die spektrophotometrische Bestimmung von Wasserstoffperoxid im Konzentrationsbereich von 1–65Mol/l.

     

Temperature dependence of the quadrupole splitting and μeff for [FeCl2(Dena)4]·DmgH2

Mössbauer spectrometry and magnetochemical methods have been applied to a complex known as catene: -dimethylglyoxime dichlorotetra(N,N-diethylnicotinamide) iron· (II) [FeCl₂(Dena)₄]·DmgH₂, where Dena is N,N,diethylnicotinamide and DmgH₂ is dimethylglyoxime. The compound has a high-spin state for the iron(II) (S=2). The magnetic susceptibility follows the Curie-Weiss law with a small value of , The E_Q=f(T) relation shows that the symmetry of the immediate environment of the iron is less than tetragonal: ₁=190 cm^–1, ₂=490 cm^–1.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, No. 1, pp. 56–60, January–February 1992.     

Extraction-spectrophotometric determination of traces of copper(II), zinc(II), cadmium(II) and mercury(II) with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol

Summary Sensitive extraction-spectrophotometric procedures are described for the complexes of Cu(II), Zn(II), Cd(II) and Hg(II) with 5-Br-PADAP using chloroform as solvent. Optimal conditions have been established for the quantitative extraction of the metal chelates and their composition and optical characteristics have been determined as well. The conditional extraction constants amount logK _ex=10, the molar absorptivities of the complexes being 10⁵ l·mole^–1·cm^–1. Job's method and equilibrium shift method indicate the molar ratios M5-Br-PADAP=12.

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Spektralphotometrische Bestimmung von Spuren Cu(II), Zn(II), Cd(II) und Hg(II) mit 2-(5-Bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP)

Zusammenfassung Einfache und empfindliche Methoden zur extraktionsspektralphotometrischen Bestimmung von Spuren Cu(II), Zn(II), Cd(II) und Hg(II) mit 5-Br-PADAP wurden beschrieben. Chloroform wurde als Extraktionsmittel verwendet. Die optimalen Bedingungen für die quantitative Extraktion der Metallchelate wurden ermittelt und deren Zusammensetzung bestimmt. Die Stabilitätskonstanten haben hohe Werte (logK _ex=10), die molare Absorption der Komplexe beträgt 10⁵1·mol^–1·cm^–1. Das Molarverhältnis der Komplexe beträgt M5-Br-PADAP=12.

     

Extraction-spectrophotometric determination of iron with 2-(2′-benzothiazolylazo)-4,6-dimethylphenol

An extraction-spectrophotometric method for the determination of trace amounts of iron based on its extraction into chloroform with 2-(2-benzothiazolylazo)-4,6-dimethylphenol (BTADMP) from a pH 6.5 medium has been developed. The extracted 12 FeBTADMP complex species allow the determination of 4–30gmg of iron (=3.92×10⁴1·mol^–1·cm^–1 at 790 nm). The method is highly selective and has been applied to the determination of iron in polymineral-polyvitamin pharmaceutical products.     

The supramolecular structures and reactivities of some complexes of chiral crown ethers with borane ammonia

Whereas 1 1 crystalline complexes have been isolated between borane ammonia and methyl 4,6-O-benzylidene-2,3-dideoxy--d-galactopyranosido [2,3-b]-1,4,7,10,13,16-hexaoxacyclo-octadecane (1), methyl 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido [2,3-b] (methyl 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido [2,3-k]-1,4,7,10,13,16-hexaoxacyclo-octadecane (3), and (1R,2R,7R,24R)-3,5,8,11,14,17,20,23,26,28-decaoxatricyclo-[21.4.0.0^2,7]octacosane (4), the hosts, methyl, 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido[2,3-b] 1,4,7,10,13,16-hexaoxacyclo-octadecane (2) and 1,4 1,4 3,6 3,6-tetra-anhydro-2,2 5,5-bis-O-oxydiethylenedi-d-mannitol (5) have yielded 2 1 (guest:host) crystalline complexes with borane ammonia as guest. X-ray analyses of the supramolecular structures of BH₃NH₃ ·1, (BH₃NH₃)₂ ·2, BH₃NH₃ ·3, BH₃NH₃ ·4, and (BH₃NH₃)₂ ·5 have been carried out and BH₃NH₃ ·1, BH₃NH₃ ·2, and (BH₃NH₃)₂ ·5 have been shown to reduce acetophenone with enantiomeric excesses of 5, 13, and 10% respectively. Supplementary Data relating to this article (atomic coordinates of the hydrogen atoms and thermal parameters) are deposited with the British Library as Supplementary Publication No. SUP 82017 (74 pages).Dedicated to Professor H. M. Powell.     

Konformations-Enatiomerie, 3. Mitt.: Kinetik und thermodynamische Daten der Racemisierung von optisch aktivem 4,5-6,7-Dibenzo-1,2-dithia-cyclooctadien

Zusammenfassung Die Racemisierung der im Titel genannten, in Konformations-Enantiomere gespaltenen Verbindung (I) wird kinetisch untersucht. Aus der Temperaturabhängigkeit der Geschwindigkeitskonstanten werden die Aktivierungsparameter:E =27,3±±0,6, H=26,6±0,6, G=28,8±0,2 kcal/Mol und S=–6,0±2,2 kcal/Mol·Grad bestimmt. Die Konformationen und die Ursachen für ihre hohe Stabilität werden diskutiert.Mit 5 AbbildungenHerrn Prof. Dr.F. Wessely zum 70. Geburtstag gewidmet.2. Mitt.:A. Lüttringhaus undK. C. Peters, Angew. Chem.78, 603 (1966).     

Exciton Chirality. (A) Origins of and (B) Applications from Strongly Fluorescent Dipyrrinone Chromophores

Summary. (A) The origin of exciton interaction and examples of its application to organic stereochemistry are presented. (B) N,N-Carbonyl-bridged dipyrrinones constitute a new class of highly fluorescent chromophores suitable for investigations of stereochemistry and absolute configuration. N,N-Carbonylxanthobilirubic acid esters are strongly fluorescent, with a fluorescence quantum yield (_F) 0.8, but produce only weak exciton CD from the trans-1,2-cyclohexanediol template. The ester of an analog with benzoic acid replacing propionic, N,N-carbonyl-8-(4-carboxyphenyl)-3-ethyl-2,7,9-trimethyl-(10H)-dipyrrin-1-one, exhibits strong fluorescence (_F=0.68, _em=493nm, _ex=422nm in CHCl₃) and UV-Vis absorption (21000 at 424nm) in organic solvents. Its diester with (1S,2S)-cyclohexanediol is fluorescent and exhibits exciton circular dichroism (=+15dm³·mol^–1·cm^–1, =432nm; =–4dm³·mol^–1cm^–1, =380nm) that correlates with the Exciton Chirality Rule.     

MD Simulation of an Infinitely Dilute Aqueous Solution of Formamide. Study of Thermodynamic, Structural, Dynamic, and Spectroscopic Properties

A molecular dynamics simulation of an infinitely dilute aqueous solution of formamide was carried out using an MP2-CP ab initio potential to describe the solute–solvent interaction. Various static and dynamic properties were calculated using this potential obtained by fitting the formamide–water interaction energies to a 12-6-1 type function. These energies were calculated with the supermolecular approach by considering the MP2 correlation and the CP superposition. The values presented for the thermodynamic functions (H _S–W = –25.5 kcal-mol^–1 and G _S–W = –15.9 kcal-mol^–1), the structure of the first hydration layer (with 5 to 6 solvent molecules bonded to the solute), the solute's translational (D= 1.50 × 10^–5 cm²-s^–1) and rotational ( = 6.6 ps) mobility in the surrounding medium, and the positions of the H···O hydrogen bond spectral bands corresponding to these motions (_i = 92, 246, 379, and 636 cm^–1), are in agreement with the available results for this and other similar systems. In addition, the results are compared with those obtained by using parameters transferred from other systems. We observed that these values depend strongly on the potential used and concluded that it is advisable to avoid the use of such parameters.     

Amplification method for the spectrophotometric determination of phosphorus

An amplification method with ion-exchange pre-separation for the spectrophotometric phosphorus determination in various alloys is described. Phosphorus is converted into molybdophosphoric acid, separated by selective extraction and back-extracted into the aqueous phase. The molybdenum is liberated by alkaline decomposition of the heteropoly acid. The spectrophotometric measurement is based on the reaction of molybdenum(VI) with 2,2-biquinoxalyl. High molar absorptivity of 1,1-dihydro-2,2-biquinoxalylene (=3.3 · 10⁴ L mol^–1 cm^–1) and the twelve-fold amplification guarantee high precision and makes the determination of phosphorus in the 1–6 g level possible.     

Additive prediction of thermodynamic functions of hydrofluorides

Summary The experimental data available on the thermodynamic functions ⁰ forMF·nHF hydrofluorides [M=Li, Na, K, Rb, Cs, NH₄, Ag(I) and Tl(I);n=1–3] have been evaluated additively. The unknown values of ⁰ forn=0÷7 are predicted.

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Additive Voraussagen der thermodynamischen Funktionen von Hydrogenfluoriden (Kurze Mitt.)

Zusammenfassung Die vorhandenen experimentellen Daten über die thermodynamischen Funktionen ⁰ von HydrogenfluoridenMF·nHF [M=Li, Na, K, Rb, Cs, NH₄, Ag(I) und Tl(I);n=1–3] werden linear ausgeglichen und die fehlendenden Werte für ⁰ mitn=0÷7 vorausgesagt.

     

Some remarks on the periodical change of the stability constants of the lanthanide complexes

The correlations between the values of the lgK (K = stability constant of the lanthanide complex) and the reciprocal of the ionic radius 1/r or the sum of the ionization potentials ₁ ³ I for the lanthanide ions were reviewed for different ligands. A straight-line relationship (lgK – lgK)/lgK vs. (1/r – 1/r)/(1/r) or vs. ( ₁ ³ I – ₁ ³ I)/ ₁ ³ I was found within the tetrads La-Nd, Gd-Ho, and Er-Lu.

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Bemerkungen zum periodischen Wechsel der Stabilitätskonstanten von Lanthaniden-Komplexen

Zusammenfassung Es wurde eine Übersicht der Korrelationen zwischen den Werten von logK (K = Stabilitätskonstante der Lanthanidenkomplexe) und den reziproken Ionenradien 1/r oder der Summe der Ionisierungspotentiale ₁ ³ I für die Lanthanidenionen für verschiedene Liganden gegeben. Dabei wurde eine lineare Korrelation für (lgK – lgK)/lgK gegen (1/r – 1/r)/(1/r) oder gegen ( ₁ ³ I – ₁ ³ I)/_1/3 I innerhalb der Tetraden La-Nd, Gd-Ho und Er-Lu aufgefunden.

     

Simultaneous spectrophotometric determination of molybdenum and iron with salicylaldehyde thiosemicarbazone,and application to the analysis of steels

Summary Salicylaldehyde thiosemicarbazone reacts with molybdenum (VI) in mineral acid solution, in the presence of stannous chloride, to produce a 11 red-violet complex (_max=520 nm,=4.8×10³l·mole^–1·cm^–1). Iron(II and III) forms a green 12 complex, in ammonia-ammonium chloride solution (_max=590 nm,=1.7×10³l· mole^–1·cm^–1). Both complexes have been used with success in the photometric estimation of molybdenum and iron in mixtures. Molybdenum may be determined in presence of 40 times its weight of iron. Iron may be determined in presence of twice its weight of molybdenum. The reagent can be applied to the analysis of steels. The interferences of some metallic ions have been examined.

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Zusammenfassung Salicylaldehydsemicarbazon reagiert mit Molybdän(VI) in mineralsaurer Lösung in Gegenwart von Zinn(II)chlorid unter Bildung eines rot-violetten 11-Komplexes (_max=520 nm;=4,8·10³ l·Mol^–1·cm^–1). Eisen (II und III) bildet einen grünen 12-Komplex in einer Ammoniak-Ammoniumchloridlösung (_max=590nm;=l,7·10³ l·Mol^–1·cm^–1). Beide Komplexe eignen sich zur photometrischen Bestimmung von Mo und Fe in Gemischen. Mo kann in Gegenwart der 40fachen Gewichtsmenge Fe bestimmt werden, Fe läßt sich neben der doppelten Gewichtsmenge Mo bestimmen. Das Reagens eignet sich für die Stahlanalyse. Störungen durch metallische Fremdionen wurden überprüft.

     

Spectrophotometric determination of vanadium with 4-(1′H-1′,2′,4′-Triazolyl-3′-azo)-2-methylresorcinol

Summary 4-(1H-1,2,4-Triazolyl-3-azo)-2-methylresorcinol reacts with vanadium(V) at pH 8.10 (Tris-HClO₄ buffer solution) to produce a pink-violet 11 complex ( _max=525 nm,=2.55×10⁴l·mol^–1· cm^–1) in a 50% (v/v) methanol-water medium, which allows the spectrophotometric determination of 0.1 to 1.51 ppm of vanadium. The method has been applied for the determination of the vanadium content in low alloy steels.

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Spectrophotometriscbe Bestimmung von Vanadin mit 4-(1H-1,2,4-triazo-lyl-3-azo)-2-methylresorcin

Zusammenfassung Vanadin bildet bei pH 8,10 (Tris-HClO₄-buffer) mit 4-(1H-1,2,4-tri-azolyl-3-azo)-2-methylresorcin ein rosenrot-violettes Chelat, dessen Absorptionsmaximum bei 525 nm in Gegenwart von 50% Methylalkohol gemessen wird. Dieser 11-Komplex entspricht bei einer Vanadin-Konzentration von 0,1–1,51g/ml dem Beerschen Gesetz; seine molare Absorptivität ist 2,55×10⁴l·mol^–1·cm^–1. Das Verfahren wurde zur Bestimmung des Vanadins in Stahl verwendet.

     

Path of “dry” electrons before localization in liquid hydrocarbons

Conclusions On the basis of measurements of values of in liquid hydrocarbons, it has been shown that the path length before localization of a photoliberated electron increases with increasing mobility of the excess electron, from approximately 40 Å (methylcyclohexane) to 200 Å (isooctane). In a liquid with10^–2 cm²/V·sec (methylcyclohexane, hexane), the localization takes place before or immediately after thermalization of the electron. In a liquid with>10^–1 cm²/V·sec, the electron passes through the main part of its path before localization, being in thermal equilibrium with the medium.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2198–2203, October, 1985.     

Kinetics and mechanism of isothermal dehydration of LiKC4H4O6 · H2O single-crystals

The kinetics of isothermal dehydration of LiKC₄H₄O₆.H₂O single-crystals was investigated in the [001] crystallographic direction under a dynamic vacuum of 6.7×10^–5 Pa with a quartz crystal microbalance. The removal of H₂O molecules may be described by a diffusion equation for a semi-infinite medium. The diffusion coefficients vary from 2.13×10^–11 cm² s^–1 at 391.7 K to 9.9×10^–9 cm² s^–1 at 453.2 K. The scanning electron microscope data provide some evidence that the dehydration is not a topochemical reaction. From the experimental data it is concluded that the anhydrous product is in the state of premelting. This explains the anomalous diffusion energyE _D=37±1 kcal mol^–1 and preexponential factorD ₀=5×10⁹ cm² s^–1.

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Zusammenfassung Die Kinetik der Entwässerung von LiKC₄H₄O₆.H₂O in [001] — Richtung unter dynamischem Vakuum wurde mit einer Quarzkristall-Mikrowaage verfolgt. Die Abgabe von Wasser kann mit einer Diffusionsgleichung für ein halb-unendliches Medium beschrieben werden, die Diffusionskoeffizienten variieren von 2, 13 · 10^–11 cm²s^–1 bei 391,7 K bis 9,9 · 10^–9 cm² s^–1 bei 453,2 K. Rasterelektronenmikroskopische Aufnahmen zeigen, daß die Entwässerung nicht topochemisch abläuft. Nach dem experimentellen Ergebnis befindet sich das entwässerte Produkt in einem Vorschmelz-Stadium. Daraus erklären sich die anomalen Werte für die DiffusionsenergieE _D=(37±1) kcal mol–1 und den präexponentiellen FaktorD ₀=5 · 10⁹ cm² s^–1.

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6,7 · 10. LiKC₄H₄O₆.H₂O [001]. . 2,13·10^{–11 2 –1} 391,7 9,9·10^{–9 2 –1} 453,2 . , . , «», E =37±1 ·^{– 1} ₀=5·10⁹²·^–1.

     

Effect of the state of vanadium cations on the IR spectra of adsorbed carbon monoxide

ESR and IR-spectrosocpic studies of the effect of the state of vanadium ions on the IR-spectra of adsorbed CO have revealed complex formation of CO with V⁴⁺ (vCO at 2192 and 2205 cm^–1) and V³⁺ (vCO at 2178 and 2185 cm^–1) ions.

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-- - CO. CO V⁴⁺ (vCO 2192, 2205 cm^–1) V³⁺ (vCO 2178, 2185 cm^–1).