DC Electrical Conductivity of the Direct Electrochemically Synthesized Polythiophene Metal Complexes

Electrochemical anodic oxidation of a metal anode in an acetone solution of 2,5-diamino-3,4-dicyanothiophene gave the polythiophene metal complexes of Co, Ni, Cu, Zn, Cd, and Sn. Chemical analyses, as well as FTIR and electronic spectral data, are presented to confirm the formulation of the isolated materials. DC electrical conductivity measurements of the polymer complexes were measured in the range 300–500 K in the annealed and 5% doped forms. The products gave electrical conductivity in the semi-conducting region that increased by heat.     

Exploring the Reactivity of a Frustrated Sn/P Lewis Pair: The Highly Selective Complexation of the cis-Azobenzene Photoisomer

The reactivity of the geminal frustrated Lewis pair (FLP) (F₅C₂)₃SnCH₂P(tBu)₂ ( 1 ) was explored by reacting it with a variety of small molecules (PhOCN, PhNCS, PhCCH, tBuCCH, H₃CC(O)CH=CH₂, Ph[C(O)]₂Ph, PhN=NPh and Me₃SiCHN₂), featuring polar or non-polar multiple bonds and/or represent α,β-unsaturated systems. While most adducts are formed readily, the binding of azobenzene requires UV-induced photoisomerization, which results in the highly selective complexation of cis-azobenzene. In the case of benzil, the reaction does not lead to the expected 1,2- or 1,4-addition products, but to the non-stereoselective (tBu)₂PCH₂-transfer to a prochiral keto function of benzil. All adducts of 1 were characterised by means of multinuclear NMR spectroscopy, elemental analyses and X-ray diffraction experiments.     

Mehr-Detektor-Anordnung für die Koinzidenzmessung von Positronenstrahlern

Procedures are given for the title compounds, which allow their preparation in high chemical purity and without any depletion of the ¹⁵N-content. A nitrogen isotope exchange between NOBF₄ and ¹⁵N₂O₃ was found, but it is too slow for preparative purposes.     

A facile and efficient synthesis of 3‐cyanoindoles by a simple palladium(II)‐catalyzed C─H activation of indoles

An efficient trans ‐PdCl₂(NH₂CH₂COOH)₂‐catalyzed direct C3‐cyanation of indole C─H bonds is described. Notably, free (N─H)‐indoles reacted smoothly using the procedure, and the desired product 3‐cyanoindoles were obtained in good to excellent yields.     

Transformation of the gas‐phase favored O‐protomer of p‐aminobenzoic acid to its unfavored N‐protomer by ion activation in the presence of water vapor: An ion‐mobility mass spectrometry study

An ion‐mobility mass spectrometry study showed that the preferred O‐protonated form of p‐aminobenzoic in the gas phase can be converted to the thermodynamically less favored N‐protomer by in‐source collision‐induced ion activation during the ion transfer process from the atmospheric region to the first vacuum region if the humidity is high in the ion source. Upon the addition of water vapor to the nitrogen gas used to promote the solid analyte to the gas phase under helium‐plasma ionization conditions, the intensity of the ion‐mobility arrival‐time peak for the N‐protomer increased dramatically. Evidently, the ion‐activation process in the first vacuum region is able to provide the energy required to surmount the barrier to isomerize the O‐protomer to the more energetic N‐protomer. The transfer of the proton attached to the carbonyl oxygen atom of the O‐protomer to the amino group takes place by a water‐bridge mechanism. Apparently, the postionization transformations that take place during the transmission of ions from the atmospheric‐pressure ion source to the detector, via different physical compartments of low to high vacuum, play an eminent role in determining the population ratios eventually manifested at the detector.     

Density,viscosity and thermodynamic activation for viscous flow of water+sulfolane

Densities and viscosities for the system, water (W)?+?sulfolane (SFL), have been determined for the entire range of composition at temperatures ranging from 303.15 to 323.15?K. Density, excess molar volume, viscosity, excess viscosity and thermodynamic activation parameters for viscous flow have been calculated and plotted against the mole fraction of SFL. The measured properties and some of the derived properties have been fitted to appropriate polynomial equations. These have been explained in terms of such factors, as, dipole–dipole interaction, partial accommodation of water molecules into the structural network of SFL and H-bonding between SFL and H₂O.     

Coordinatively Unsaturated Amidotitanocene Cations with Inverted σ and π Bond Strengths: Controlled Release of Aminyl Radicals and Hydrogenation/Dehydrogenation Catalysis

Cationic amidotitanocene complexes [Cp₂Ti(NPhAr)][B(C₆F₅)₄] (Cp=η⁵-C₅H₅; Ar=phenyl ( 1 a ), p-tolyl ( 1 b ), p-anisyl ( 1 c )) were isolated. The bonding situation was studied by DFT (Density Functional Theory) using EDA-NOCV (Energy Decomposition Analysis with Natural Orbitals for Chemical Valence). The polar Ti−N bond in 1 a–c features an unusual inversion of σ and π bond strengths responsible for the balance between stability and reactivity in these coordinatively unsaturated species. In solution, 1 a–c undergo photolytic Ti−N cleavage to release Ti(III) species and aminyl radicals ⋅ NPhAr. Reaction of 1 b with H₃BNHMe₂ results in fast homolytic Ti−N cleavage to give [Cp₂Ti(H₃BNHMe₂)][B(C₆F₅)₄] ( 3 ). 1 a–c are highly active precatalysts in olefin hydrogenation and silanes/amines cross-dehydrogenative coupling, whilst 3 efficiently catalyzes amine-borane dehydrogenation. The mechanism of olefin hydrogenation was studied by DFT and the cooperative H₂ activation key step was disclosed using the Activation Strain Model (ASM).     

Iridium-Catalyzed Formyl-Selective Deuteration of Aldehydes

We report the first direct catalytic method for formyl-selective deuterium labeling of aromatic aldehydes under mild conditions, using an iridium-based catalyst designed to favor formyl over aromatic C−H activation. A good range of aromatic aldehydes is selectively labeled, and a one-pot labeling/olefination method is also described. Computational studies support kinetic product control over competing aromatic labeling and decarbonylation pathways.