Subregular Representations of {\mathfrak{s}}{\mathfrak{l}}_n and Simple Singularities of Type A n−1

Alexander Premet has stated the following problem: what is a relation between subregular nilpotent representations of a classical semisimple restricted Lie algebra and non-commutative deformations of the corresponding singularities? We solve this problem for type A.     

Polyfunctional compounds containing the 4,6-dialkoxy-7-arylthioheptene moiety as synthetically useful intermediates. The course of lewis acid-induced transformations

Data on the selectivity of the Lewis acids induced transformations of the title compounds are presented, and the routes leading to formation of products containing either cyclohexane or 1,3-diene units are described.     

Synthesis of functionalized m-bistrifluoromethylbenzenes via cyclocondensation of 1,1,1,5,5,5-hexafluoroacetylacetone with enamines

The reaction of 1,1,1,5,5,5-hexafluoroacetylacetone with push-pull enamines having a methyl group at the α-position was investigated. It was found that the reaction is sensitive both to the structure of enamines and to reaction conditions. As a result, a set of bistrifluoromethyldialkylanilines and ethyl bistrifluoromethylsalicylate was prepared. Plausible mechanisms and factors influencing the course of the reaction are discussed.     

The solvation of iodine anions in water clusters: PES studies

We have measured the photoelectron-spectra of I^? (H₂O)_n clusters in the size range n=1–60. We have found that the first six water molecules form a solvation layer with an average 0.35 eV electrostatic stabilization of the anion. At larger cluster sizes the electrostatic stabilization of water does not fit a continuous dielectric solvent. The most stable structures of the clusters consist of internally solvated anions. In the size range n=34–40 we have found evidence for existence of cluster structures with surface solvated anions.     

Ferromagnetism in colloidal Mn2+ -doped ZnO nanocrystals

High-temperature hydrolysis of Zn(II) and Mn(II) alkoxides in a high boiling point solvent in the presence of surfactants was used to prepare surfactant-coated Zn(1-x)Mn(x)O nanocrystals with average size of 5.5 nm and x = 0.04 +/- 0.03. The magnetic properties of the nanocrystals were measured both for isolated particles diluted in a hydrocarbon matrix and for a nanocrystal powder. Nanocrystals of manganese oxide and ZnO coated with manganese oxide were prepared for comparison to the Zn(1-x)Mn(x)O nanocrystals. We find that the manganese ions primarily substitute zinc ions in the hexagonal ZnO lattice, and part of them are ferromagnetically coupled up to room temperature even in isolated noninteracting nanocrystals. The rest of the ions are magnetically disordered or uncoupled. Surprisingly, these small Zn(1-x)Mn(x)O nanocrystals poses relatively large low-temperature magnetic coercivity and relatively high blocking temperature in the isolated form, which indicate large magnetic anisotropy. In the nanocrystal powder the coercive field decreased significantly. This study highlights the advantages of working with noninteracting single domain particles of these intriguing materials.     

Thin‐Film Infrared Spectroscopy of Acetonitrile

Acetonitrile and [D₃]acetonitrile in the vicinal region of a planar AgX fiber contain linear dipole–dipole linked oligomers as shown by 1) comparison of infrared band intensity ratios in the gaseous and condensed phases and 2) remarkable plots of absorbance (C? N stretch) versus time during evaporation from an AgX planar fiber element. The plots (CH₃CN 2252 cm^?1, CD₃CN 2262 cm^?1) reveal the presence of octamers, hexamers, tetramers, and dimers along with some heptamer, trimer, and monomer structures. A novel isotope effect arises from the somewhat smaller size of the CD₃CN resulting in an increase in the CN band intensity. The organized oligomers may be termed pseudocrystals and are the main components responsible for absorption intensity in the infrared spectrum of acetonitrile, on the AgX planar fiber or in an IR cell.     

Highly selective mono-substitution in Pd-catalyzed cross-coupling reactions of 3,6-dichloropyridazine with organozinc compounds

Pd-catalyzed cross-coupling reactions of 3,6-dichloropyridazine (1) with benzyl, aryl, and alkyl organozinc compounds led to selective mono-substitution of one of the chlorine atoms. The subsequent cross-coupling of the resulting monochlorides with RZnCl afforded unsymmetrical 3,6-carbon-disubstituted pyridazines.     

The electronic structure of FeV-cofactor in vanadium-dependent nitrogenase

The electronic structure of the active-site metal cofactor (FeV-cofactor) of resting-state V-dependent nitrogenase has been an open question, with earlier studies indicating that it exhibits a broad S = 3/2 EPR signal (Kramers state) having g values of ∼4.3 and 3.8, along with suggestions that it contains metal-ions with valencies [1V³⁺, 3Fe³⁺, 4Fe²⁺]. In the present work, genetic, biochemical, and spectroscopic approaches were combined to reveal that the EPR signals previously assigned to FeV-cofactor do not correlate with active VFe-protein, and thus cannot arise from the resting-state of catalytically relevant FeV-cofactor. It, instead, appears resting-state FeV-cofactor is either diamagnetic, S = 0, or non-Kramers, integer-spin (S = 1, 2 etc.). When VFe-protein is freeze-trapped during high-flux turnover with its natural electron-donating partner Fe protein, conditions which populate reduced states of the FeV-cofactor, a new rhombic S = 1/2 EPR signal from such a reduced state is observed, with g = [2.18, 2.12, 2.09] and showing well-defined ⁵¹V (I = 7/2) hyperfine splitting, a_iso = 110 MHz. These findings indicate a different assignment for the electronic structure of the resting state of FeV-cofactor: S = 0 (or integer-spin non-Kramers state) with metal-ion valencies, [1V³⁺, 4Fe³⁺, 3Fe²⁺]. Our findings suggest that the V³⁺ does not change valency throughout the catalytic cycle.

Active site FeV-cofactor of the V-nitrogenase and the EPR spectrum of the reduced cofactor showing ⁵¹V-hyperfine coupling.     

Functionalized nanodiamonds part I. An experimental assessment of diamantane and computational predictions for higher diamondoids

The structures, strain energies, and enthalpies of formation of diamantane 1, triamantane 2, isomeric tetramantanes 3-5, T(d)-pentamantane 6, and D(3d)-hexamantane 7, and the structures of their respective radicals, cations, as well as radical cations, were computed at the B3LYP/6-31G* level of theory. For the most symmetrical hydrocarbons, the relative strain (per carbon atom) decreases from the lower to the higher diamondoids. The relative stabilities of isomeric diamondoidyl radicals vary only within small limits, while the stabilities of the diamondoidyl cations increase with cage size and depend strongly on the geometric position of the charge. Positive charge located close to the geometrical center of the molecule is stabilized by 2-5 kcal mol(-1). In contrast, diamondoid radical cations preferentially form highly delocalized structures with elongated peripheral C-H bonds. The effective spin/charge delocalization lowers the ionization potentials of diamondoids significantly (down to 176.9 kcal mol(-1) for 7). The reactivity of 1 was extensively studied experimentally. Whereas reactions with carbon-centered radicals (Hal)(3)C(*) (Hal=halogen) lead to mixtures of all possible tertiary and secondary halodiamantanes, uncharged electrophiles (dimethyldioxirane, m-chloroperbenzoic acid, and CrO(2)Cl(2)) give much higher tertiary versus secondary selectivities. Medial bridgehead substitution dominates in the reactions with strong electrophiles (Br(2), 100 % HNO(3)), whereas with strong single-electron transfer (SET) acceptors (photoexcited 1,2,4,5-tetracyanobenzene) apical C(4)-H bridgehead substitution is preferred. For diamondoids that form well-defined radical cations (such as 1 and 4-7), exceptionally high selectivities are expected upon oxidation with outer-sphere SET reagents.