Coordination Compounds of Copper(II) with Bis(5-amino-1,2,4-triazol-3-yl)alkanes

Procedures for synthesis of coordination compounds of copper(II) with bis(5-amino-1,2,4-triazol-3-yl)alkanes as ligands. A conclusion was drawn that the coordination polyhedron of copper(II) has different configurations depending on the structure of the ligand and on the coordination mode.     

Syntheses of a Cp'Re=S derivative and more complex products

The reaction of Cp'ReCl(2)S(3) (Cp' = Me(4)EtC(5)) with slightly less than 2 equiv of a phosphine reagent results in the formation of [Cp'Re(Cl)(2)(mu-S)](2), 2, which has been characterized by an X-ray diffraction study. Reactions of 2 with nucleophiles did not lead to monomeric derivatives of the type Cp'ReS(Cl)(2)(Nuc). The reaction of Cp'ReCl(2)(SC(2)H(4)S) with (Me(3)Si)(2)S resulted in the formation of three new products: Cp'ReS(SC(2)H(4)S), 4; Cp'Re(S(3))(SC(2)H(4)S), 5; and a tetranuclear derivative, [(Cp'Re)(2)(mu-S)(mu,eta(2)-SC(2)H(4)S)(mu,eta(1)-SC(2)H(4)S](2)Cl(2), 6. Complexes 4 and 6 have been characterized by X-ray diffraction studies. The electrochemical properties of the mononuclear Re=S derivative, 4, are compared with those of Re=O and Re=NR analogues.     

Spectroscopic, thermal and electrochemical studies on some nickel(II) thiosemicarbazone complexes

Several complexes of thiosemicarbazone derivatives with Ni(II) have been prepared. Structural investigation of the ligands and their complexes has been made based on elemental analysis, magnetic moment, spectral (UV-Vis, i.r., (1)H NMR, ms), and thermal studies. The i.r. spectra suggest the bidentate mononegative and tridentate (neutral, mono-, and binegative) behavior of the ligands. Different stereochemistries were suggested for the isolated complexes. The thermogravimetry (TG) and derivative thermogravimetry (DTG) have been used to study the thermal decomposition and kinetic parameters of some ligands and complexes using the Coats-Redfern and Horowitz-Metzger equations. The redox properties and stability of the complexes toward oxidation waves explored by cyclic voltammetry are related to the electron withdrawing or releasing ability of the substituent of thiosemicarbazone moiety. The samples displayed Ni(II)/Ni(I) couples irreversible waves associated with Ni(III)/Ni(II) process.     

Substitution and condensation reactions with poly(anilineboronic acid): reactivity and characterization of thin films

Poly(anilineboronic acid) thin films are treated under various conditions to achieve substitution or condensation reactions involving the boronic acid moiety. These reactions are studied with polarization modulated infrared reflection absorption spectroscopy, cyclic voltammetry, and UV-vis spectroscopy. The results suggest the single-step formation of substituted polyanilines, such as poly(hydroxyaniline), halogenated polyanilines, and mercury chloride-substituted polyaniline. A condensation reaction of poly(anilineboronic acid) with cis-diol compounds in aqueous solution, as well as with phenylenebisboronic acid and salycilamide in THF, indicates the formation of boronic esters. The latter reactions appear to be a good entry point for the formation of complex or supramolecular polymer structures.     

Crystal and molecular structures of the complexes of cobalt dichloride with 1-isopropenylimidazole and 1-vinylimidazole

The crystal and molecular structures of bis(1-isopropenylimidazole)dichlorocobalt (C₁₂H₁₆Cl₂·N₄Co) [R 0.036 (R _W 0.089) for 3229 unique reflections with I > 2σ(I)] and tetra(1-vinylimidazole)dichlorocobalt (C₂₀H₂₄Cl₂N₈Co) [R 0.031 (R _W 0.072) for 1863 unique reflections with I > 2σ(I)] were determined. In these molecular complexes, the monodentate terminal 1-alkenylimidazole ligands coordinate to the metal via a “pyridine” nitrogen atom. In C₁₂H₁₆Cl₂N₄Co, the Co atom has a distorted tetrahedral 2N,2Cl coordination. The coordination polyhedron of cobalt in C₂₀H₂₄Cl₂N₈Co is a strongly elongated 4N,2Cl octahedron. The Co-N and Co-Cl bonds [Co-N 2.015(2) and 2.032(4) Å; Co-Cl 2.229(2) Å] in the tetrahedral complex C₁₂H₁₆Cl₂N₄Co are shorter than those in the octahedral complex C₂₀H₂₄Cl₂N₈Co [Co-N 2.134(2) and 2.157(2) Å; Co-Cl 2.518(1) Å]. In the structures of both complexes there are short contacts involving the Cl atoms.     

Bayesian analysis and inference from QSAR predictive model results

QSAR models have been under development for decades but acceptance and utilization of model results have been slow, in part, because there is no widely accepted metric for assessing their reliability. We reapply a method commonly used in quantitative epidemiology and medical decision-making for evaluating the results of screening tests to assess reliability of a QSAR model. It quantifies the accuracy (expressed as sensitivity and specificity) of QSAR models as conditional probabilities of correct and incorrect classification of chemical characteristic, given a true characteristic. Using Bayes formula, these conditional probabilities are combined with prior information to generate a posterior distribution to determine the probability a specific chemical has a particular characteristic, given a model prediction. As an example, we apply this approach to evaluate the predictive reliability of a CATABOL model and base on it a "ready" and "not ready" biodegradability classification. Finally, we show how predictive capability of the model can be improved by sequential use of two models, the first one with high sensitivity and the second with high specificity.     

Kinetics of the hydroxylation of N-picryl-4-[4-(dimethylamino)styryl]pyridinium salts by molecular oxygen in acetonitrile

The reactions of N-picryl-4-[4-(dimethylamino)styryl]pyridinium salts with molecular oxygen in the presence of 4-[4-(dimethylamino)styryl]pyridine (DASP) in acetonitrile proceeds with the formation of DASP picrate. The reactions are first-order relative to the salt cation, molecular oxygen, and the catalyst (DASP). L. M. Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine, 70 R, Lyuksemburg ul., Donetsk 340114, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 34, No. 5, pp. 286–289, September–October, 1998.     

Nitropyrazoles

The double Vilsmeier formylation of theC-methyl group in pyrazole derivatives has been shown to occur when a nitro-group is in the adjacent position of the ring. A method for the synthesis ofC-(diformylmethyl)nitropyrazoles based on this reaction has been developed.For the previous communication, see Ref. 1; for Part 2, see Ref.2 Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1273–1276, July, 1993.     

Singlet–triplet splittings as obtained from the Xα-scattered wave method: A theoretical analysis

The theoretical determination of singlet–triplet splittings of the excited states of closed-shell molecules is discussed with emphasis on the use of the Xα–scattered wave method. With this method, splittings can be computed in two independent ways. Both will have corrections due to orbital relaxation effects. The singlet–triplet splittings obtained with the Xα–scattered wave method for several large organic molecules are reviewed. It is seen that the results using the two splitting formulas differ by a large amount; in fact, they differ by the magnitude of the computed splitting. We provide a criterion for choosing the results obtained with one method over the other by showing that they both give upper bounds to the best result obtainable within the framework of the model. However, because of the large differences between the two methods, the quantitative value of the splitting should be viewed with caution.     

Exact spin-pairing energies at the crossovers in octahedral d 4, d 5, d 6, and d 7 transition metal complexes

Exact spin-pairing energies are calculated by direct diagonalization of the relevant ligand field plus interelectronic repulsion matrices for the configurations d ⁴, d ⁵, d ⁶, and d ⁷ of octahedral transition metal ions. The results are presented in terms of /B as function of = C/B for the range of values =3.0 to 8.0. Comparison with the quantity resulting from a simplified approach in which configuration interaction is neglected or considered on an approximate basis only reveals significant differences. Useful estimates of spin-pairing energies are provided, in addition, on the basis of empirical magnetic and electronic spectral data.

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Zusammenfassung Exakte Spinpaarungsenergien für die Konfigurationen d ⁴, d ⁵, d ⁶ und d ⁷ oktaedrischer Übergangsmetallionen werden durch direkte Diagonalisierung der entsprechenden Matrizen des Ligandenfeldes sowie der Elektronenwechselwirkung berechnet. Die Ergebnisse für /B werden in Abhängigkeit von = C/B für den Wertebereich =3.0 bis 8.0 angegeben. Ein Vergleich mit der Größe , die bei einer vereinfachten Behandlung unter Vernachlässigung oder näherungsweiser Berücksichtigung der Konfigurationswechselwirkung erhalten wird, zeigt auffallende Unterschiede. Nützliche Abschätzungen der Spinpaarungsenergie werden außerdem unter Benutzung empirischer magnetischer und elektronenspektroskopischer Daten erhalten.

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Résumé Les énergies exactes de couplage de spin sont calculées par diagonalisation directe du champ de ligand correspondant en plus des matrices de répulsion électronique pour les configurations d ⁴, d ⁵, d ⁶ et d ⁷ des ions octaédriques des métaux de transition. Les résultats sont présentés en termes de /B en fonction de = C/B dan l'intervalle =3,0 à 8,0. On trouve des différences significatives par comparaison de avec les valeurs résultant d'une approche simplifiée sans interaction de configuration ou avec interaction de configuration approchée. De plus, des estimations des énergies de couplage de spin sont obtenues à partir de données empiriques magnétiques et spectrales.