Charge transfer complexes and salts of ionenes

A review of the synthesis and properties of ionenes is presented. Particular attention is paid to the electrical and related properties of conductive teteracyano-p-quinodimethane (TCNQ) complex salts of ionenes containing ammonium or sulfonium groups in the main chain and to their chemical stability. The recent work on preparation of such ionenes with inorganic and organic counterions which show interesting linear and nonlinear optical properties is also discussed. It is shown that in the solid state ionenes act as a kind of a matrix fixing, in a chemically controlled way, positions and distribution of different kinds of counterions. Because the reaction of counterion exchange is easy in the case of ionenes it provides a convenient way to prepare a broad class of polyelectrolytes with many different properties.     

Synthesis and transformations of metallacycles 33. The first example of cycloalumination of cyclonona-1,2-diene with Et<Subscript>3</Subscript>Al and EtAlCl<Subscript>2</Subscript> in the presence of Cp<Subscript>2</Subscript>ZrCl<Subscript>2</Subscript>

Catalytic cycloalumination of cyclonona-1,2-diene upon treatment with Et₃Al and EtAlCl₂ in the presence of Cp₂ZrCl₂, leading to 10-ethyl-10-aluminabicyclo[7.3.0^1,9]dodec-8-ene (1) and 11-ethyl-11-aluminatricyclo[10.7.0^1,12.0^2,10]nonadeca-9,12-diene, respectively, was accomplished in high yields. A possibility for the selective transformation of compound 1 to 1-allyl-9-(pent-4-enyl)cyclonon-1-ene and 10-hydroxybicyclo[7.3.0^1,9]dodec-8-ene in one preparative step was demonstrated. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2156–2159, November, 2007.     

Emission,Emissionslebensdauer und Absorption von [Cr urea6]X3-Einkristallen

Emission and absorption polarization spectra as well as emission lifetimes between room temperature and 5 °K have been measured of [Cr urea₆]X₃ single crystals, where X stands for ClO ₄ ^– , J^–, NO ₃ ^– , Br^–, Cl^–, F^–, and X₃ for JSO ₄ ^3– . The strong temperature dependence of the fluorescence/phosphorescence-ratios, and of the emission lifetimes is discussed. The differences between the spectra as well as the emission lifetimes of the various salts can be attributed to an anion dependent trigonal perturbation.

Die Autoren danken dem Verband der Chemischen Industrie für finanzielle Unterstützung dieser Arbeit.     

Synthesis and X-ray crystal structure of oxamido-bridged heterobinuclear Ni(Ⅱ)-Cu(Ⅱ) complexes

The two complexes [Ni(oxen)Cu(L)2](ClO4)2.xH2O (L=2,2'-bipyridyl(bpy), 1,10-phenanthroline(phen)) have been synthesized, where oxen is N,N'-bis(2-aminoethyl)oxamido di-anion. The crystal structure of [Ni(oxen)Cu(bpy)2](ClO4)2.CH3OH has been determined by X-ray diffraction method. The crystal is triclinic system, space group P1 with a=12.179(1),b=12.298(2), c=11.476(2) A, a=97.57(1), B=97.52(1), 7=80.29(2), V=1669.04(67) A3, Z=2, Dcalcd=1.667 g/cm3. The structure has been refined to final R of 0.076 and Rw of 0.080, respectively. The complexes have an extended oxamido-bridged structure and consist of Ni(Ⅱ) ion in a square planar environment and Cu(Ⅱ) ion in a distorted octahedral environment.     

Kinetic and Thermodynamic Parameters of the Thermal Decomposition of Some Metal Complexes of 4‐Benzamido‐3‐Thiosemicarbazone Derivatives

The kinetic and thermodynamic parameters such as reaction order, activation energy, enthalpy, free energy and entropy change related to the thermal decomposition of Co(II), Ni(II) and Cu(II) hydrazone complexes of 4‐benzamido‐1‐(4‐actylpyridine)‐3‐thiosemicarbazone (BACPT) and 4‐benzamido‐1‐(pyridine‐3‐aldehye)‐3‐thiosemicarb‐azone (BAPT) were evaluated from differential thermal analysis (DTA) curves using Thomas‐Clarke's method. The thermal stability of these complexes are discussed in relation to the nature of the metalion and of the ligand present. A suitable mechanism for the thermal decomposition process of the complexes based on the data of the thermogravimetric analysis (TGA) was suggested.     

Micellar effect on the electron transfer reaction of chromium(V) ion with organic sulfides

The rate of electron transfer from organic sulfides to [Cr^V(ehba)₂]⁻ (ehba-2-ethyl-2-hydroxy butyric acid) decreases with a decrease in the polarity of the medium. The anionic surfactant, SDS and the cationic surfactant, CTAB have different effects on the kinetics of this reaction. The micellar inhibition observed in the presence of SDS is probably due to the decrease in the polarity and the electrostatic repulsion faced by the anionic oxidant from the anionic micelle and the partition of the hydrophobic substrate between the aqueous and micellar phases. The micellar catalysis in the presence of CTAB is attributed to the increase in the concentration of both reactants in the micellar phase. This micellar catalysis is observed to offset the retarding effects of the less polar micellar medium and the unfavorable charge-charge interaction between the + charge developed on S center in the transition state and the cationic micelle. This catalysis is contrary to the enormous micellar inhibition observed with IO₄⁻, HSO₅⁻ and HCO₄⁻ oxidation of organic sulfides.     

Stoichiometric and catalytic methods of asymmetric synthesis of nonproteinogenic α-and β-amino acids via transition metal coordination compounds

The complexes of glycine, -alanine, and -alanine with (S)-[N-(N-benzylprolyl)amino] benzophenone formed by Ni(II) and Cu(II) ions and Schiff bases enter into different nucleophilic and electrophilic reactions with the formation of diastereoisomeric complexes which decompose into proteinogenic and nonproteinogenic L-amino acids with a high chemical yield and elevated optical purity (70–90%). Optically pure amino acids can be obtained from diastereoisomerically pure complexes after the complexes are separated by recrystallization of the mixture of diastereoisomeric complexes formed. A new type of interphase catalysts of C-alkylation of achiral Schiff bases was proposed. The catalysts are positively charged Ni(II) and Cu(II) complexes of Schiff bases of chiral diamines. In some cases, these complexes have a higher activity and capacity to execute asymmetric alkylation than traditional chiral interphase catalysts based on cinchonidine.Based on materials in the section report by Yu. N. Belokon' to the 7th European Symposium on Organic Chemistry, ESOC-7.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1106–1127, May, 1992.     

Steric effects of substituted quinolines on lithium coordination geometry

The X-ray crystal structures of a series of lithium quinolates – lithium 8-hydroxyquinolinate (Liq), lithium 2-methyl-8-hydroxyquinolinate (MeLiq), and 2-phenyl-8-hydroxquinolinate (PhLiq), are compared. The substitution at the 2-position of the 8-hydroxyquinoline ligand has significant impact on the aggregation of the lithium complex in the crystalline state. Liq and MeLiq molecules crystallize as hexamers, whereas PhLiq crystallizes as a tetramer. The possible influence of crystal-packing forces on the preferred cluster structure was probed using density functional theory calculations on a systematically varied set of Liq, MeLiq, and PhLiq clusters. For Liq and MeLiq, the observed structures match the most stable computed structures. In the PhLiq case, the observed tetrameric structure is computed to be less stable (+1.2 kcal/mol/monomer) than the lowest energy structure, a hexamer. In this case, solid-state effects probably outweigh small differences in cluster stability.     

Synthesis and investigation of mono- and binuclear cyano-bridged complexes of rhodium,ruthenium, and palladium

Binuclear Rh^III and Ru^II complexes of the [M¹-CN-M²]⁺BF ₄ ^– (M¹ and/or M² are (⁵-Cp)(³-C₃H₅)Rh and (⁶-C₆H₆)(³-C₃H₅)Ru) type, heteronuclear organometallic compound (⁵-Cp)(³-C₃H₅)RhCNPd(³-C₃H₅)Cl, and mononuclear Rh^III and Ru^II complexes [(³-C₃H₅)LM(MeCN)]⁺ _BF4 ^– (M = Rh, L = ⁵-Cp; M = Ru, L = ⁶-C₆H₆) were synthesized. An electrochemical study of these compounds in solutions demonstrates that the bond between the bridged CN ligand and the metal atoms is rather strong, and there is no dissociation into mononuclear fragments in solutions. The kinetics of the reaction of [(⁵-Cp)(³-C₃H₅)Rh(MeCN)]⁺ _BF4 ^– with halide ions was studied by electrochemical methods. The ligand exchange proceeds by a bimolecular dissociative-exchange mechanism.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 968–973, May, 1995.     

Synthesis and characterization of poly(4-vinyl,2′-carboxybensophenone)

The synthesis and characterization of poly(4-vinyl,2′-carboxybenzophenone) ion exchange resin is described. This resin displays a remarkably high capacity for Cu²⁺. Control of pH permits selective adsorption and estimation of Fe³⁺. This ion-exchanger is quite stable to loading acid washing cycles. © 1995 John Wiley & Sons, Inc.