Charge transfer complexes of electron-rich naphthalene peri-dichalcogenides with TCNQ

The electronic structures of several highly electron-rich 2,7-dimethoxynaphthalene peri-dichalcogenides were evaluated using optical and electrochemical methods, as well as by DFT calculations. Charge transfer complexes were formed with tetracyanoquinodimethane and resulted in absorption features that span from 300 nm to 1600 nm and HOMO–LUMO energy gaps as low as 0.8 eV.     

Radiative fusion from very symmetric reactions: the giant dipole resonance in the Au nucleus

The spectra of high-energy γ rays emitted by the Giant Dipole Resonance (GDR) built on moderately excited states associated with the evaporation of 0, 1 and 2 nucleons were measured in the ⁹⁰Zr + ⁸⁹Y symmetric fusion reaction. The radiative fusion data suggest statistical emission from the compound nucleus. In addition, the analysis of the high-energy γ-ray spectra associated with the different evaporation channels at the present temperature of 0.7 MeV and spin range 15–20 show a fairly narrow width of 5.0±0.35 MeV. This value is smaller than what would be expected in a nucleus where shell effects do not play a role.     

Synthesis and Structural Features of New Schiff Base Complexes of Mononuclear MnIV,Dinuclear CoIICoIII,and Tetranuclear CuII

2‐(((2‐Hydroxy‐3‐methoxyphenyl)methylene)amino)‐2(hydroxymethyl)‐1,3‐propanediol (LH₄, as abbreviation) reacts with MnCl₂ · 4H₂O, CoCl₂ · 6H₂O, and Cu(ClO₄)₂ · 6H₂O to give the new complexes [Mn(LH₂)₂] ( 1 ), [Co₂Cl(H₂O)(LH₂)₂] · 4H₂O ( 2 ), and [Cu₄(LH₂)₄(H₂O)₄] ( 3 ). Complex 1 is formed by the assembly of two molecules of the ligand with one manganese(IV) ion. In the mixed‐valence cobalt complex 2 there is an asymmetry between the coordination spheres of cobalt(II) and cobalt(III). In the tetramer 3 four copper(II) ions attain a distorted tetrahedral configuration surrounded by four molecules of the ligand.     

Evaluation of the Antioxidant Activity of Copper(II) Complexes containing Tris‐(hydroxymethyl)aminomethane (TRIS) Units

The structural analysis and the SOD‐like activity of Cu^II complexes [(Cu)(C₁₆H₁₈N₃O₅)]ClO₄ ( 1 ) and [(Cu)₄(C₃₆H₅₂N₈O₁₂)] ( 2 ) are described with ligands obtained from the condensation of picolinaldehyde and 2‐formylpyrrole with tris(hydroxymethyl)aminomethane (TRIS). Finally, complex 1 catalyzes the dismutation of superoxide efficiently with IC₅₀ values in the range of 0.43 micromolar solution, evaluated through the inhibition of the photoreduction of nitro blue tetrazolium (NBT) (superoxide dismutase assay).     

Preparation of vinylogous 2-sulfonylindolines by the palladium-catalyzed heteroannulation of o-iodoanilines with dienyl sulfones and their further transformation to indoles and carbazoles.

The palladium-catalyzed heteroannulation of o-iodoanilines with dienyl sulfones provides a convenient route to vinylogous 2-sulfonylindolines 3. The reaction proceeds in DMF/water in the presence of potassium carbonate and catalytic palladium(II) acetate and is compatible with both electron-donating and -withdrawing substituents in the para position of the aniline, and with an alkyl substituent at C-2 of the dienyl sulfone. The indolines underwent oxidation with DDQ to afford the corresponding indoles 4. The latter were then employed as dienes in Diels-Alder reactions with dimethyl acetylenedicarboxylate (DMAD), methyl propiolate, or methyl acrylate. In the case of the latter two dienophiles, the cycloadditions were highly regioselective, affording the corresponding 1,3-products (with respect to the relative positions of the sulfone and ester groups), exclusively. The cycloadducts from acetylenic dienophiles were converted to the corresponding carbazoles by elimination of the sulfone moiety with DBU, and that from methyl acrylate was subjected to reductive desulfonylation and oxidation to the corresponding carbazole with DDQ. The method thus provides access to carbazoles with various substituents at the 3-, 4-, and 6-positions.     

Preparation and electrochemical behaviour of dinuclear platinum complexes containing NCN ligands (NCN=[C6H3(Me2NCH2)2-2,6]). The crystal structure of [C6H3(Me2NCH2)2-1,3-(CC)-5]2

A series of homodinuclear Pt compounds containing the anionic, potentially terdentate NCN ligand (NCN=[C₆H₃(Me₂NCH₂)₂-2,6]⁻) or its 4-ethynyl derivative were prepared. The two platinum centres are linked together in two different fashions: (i) directly linked by an ethynyl or diethynylphenyl group (head-to-head) and (ii) indirectly bonded by a ethynyl- or butadiynyl-linked bis-NCN ligand (tail-to-tail). The reaction of the head-to-head σ,σ′-ethynylide complex {Pt}CC{Pt} ({Pt}=[Pt(C₆H₃{CH₂NMe₂}₂-2,6)]⁺) with [CuCl]_n yields {Pt}Cl and [Cu₂C₂]_n, while with [Cu(NCMe)₄][BF₄] a Cu(I) bridged complex was formed: [(η²-{Pt}CC{Pt})₂Cu][BF₄]. The results of cyclic voltammetry experiments reveal that both connection modes of the two platinum centres lead to electrochemically independent Pt–NCN units. The X-ray crystal structure analysis of the neutral, tail-to-tail bridging butadiyne bis-NCNH ligand [C₆H₃(CH₂NMe₂)-1,3-(CC)-5]₂ is reported.     

Quasi-fission — The mass-drift mode in heavy-ion reactions

The binary and ternary products from reactions of ²³⁸U beams with targets of ¹⁶O, ²⁷Al, ⁴⁸Ca, ⁴⁵Sc, ⁴⁸Ti, ⁵⁸Fe, ⁶⁴Ni and ⁸⁹Y have been recorded at 6.0 MeV/u bombarding energy with four position-sensitive avalanche detectors, operated in coincidence. A few runs at 5.4 MeV/u have also been performed. Accurate triple-differential cross sections, $\text{d}{}^3\text{σ}\text{d}\text{A}\text{d}\text{θ}{}_{\mathrm{<mtext>c.m.</mtext>}}\text{dTKE}$, are obtained for the binary events within the full range of mass A and total kinetic energy TKE, and within almost the full range of center-of-mass angle θ_c.m.. Similar cross sections are obtained with somewhat less accuracy for triple events stemming from the sequential fission of uranium-like products. The distributions are discussed in terms of quasielastic and strongly damped scattering, where the products have partially relaxed energies and negligible average drift in mass, as opposed to capture where the products emerge with fully relaxed energies after a more or less pronounced mass drift towards symmetry. Apart from the reaction with ¹⁶O, all the capture product distributions are dominated by the non-equilibrium quasi-fission (or fast fission) process. The central feature of this reaction mechanism is the evolution of the reaction complex towards mass symmetry. With the ²⁷Al target the evolution towards symmetry is almost complete, whereas the heavier targets show very broad mass distributions with clear evidence of dissociation taking place before symmetry is reached. At the same time, the cross section for quasi-fission diminishes as the target Z-value increases. With the ⁸⁹Y target the strongly damped scattering component dominates completely. The capture cross sections are discussed in terms of the extra-push concept, and the mass and angular distributions in quasi-fission are analyzed in terms of interaction time and mass rearrangement as functions of target Z-value and excess kinetic energy in the entrance channel.     

The thermal reactions of ethylene at 500°C in the presence and absence of small quantities of oxygen

Initial rates of formation of primary products have been measured in the pyrolysis of ethylene at 500°C, and a mechanism for the reaction is proposed based on the isomerization of the n?hexyl radical. Additions of oxygen in amounts less than 0.1% markedly increased the rate of formation of all products, but oxygen was not completely consumed in the reaction. It is shown that secondary initiation processes are important at very low conversions, and butene-1 is the most reactive product. Bimolecular reactions between olefins and with oxygen are important steps in the mechanism.     

The cycloaddition of ethylene to butene-2. II. Energy relations

The rate of the thermal cycloaddition of ethylene to cis-and trans-butene-2 has been measured at 663, 678, 693, and 703°K, and the energy relations between the reactants, intermediates, and products have been determined. The intermediate biradicals formed from the cis reactants and from the trans reactants were shown to be separated by a small but measurable enthalpy difference. This result further supports the conclusion of Part I that the intermediates are distinct species which retain some of the original configuration of the reactant. The significance of the results in relation to the mechanism of “forbidden” reactions is discussed.