Structural study of a new hexagonal form of tungsten trioxide

A new form of tungsten trioxide WO₃ has been obtained by dehydration of $\text{WO}{}_3\text{·}\text{1}\text{3}\text{H}{}_2\text{O}$ hydrate. The structural study was carried out from X-ray powder diffraction and selected area electron diffraction data. The crystallographic characteristics are: the hexagonal system; a = 7.298(2) Å, c = 7.798(3) Å; Z = 6. This hexagonal WO₃ is built up of slightly distorted (WO₆) octahedra sharing their corners arranged in six-membered rings in layers normal to the hexagonal axis; stacking of such layers leads to formation of large hexagonal tunnels. Some confirmations of this structure were made by high-resolution electron microscopy. Powder X-ray diffraction allowed us to determine an average structure. Absence of suitable single crystals has not permitted us to perform a complete structural determination. Although the existence of such a hexagonal structure for pure WO₃ had been considered as likely, it had not been hitherto observed.     

Electrophilic reactions of chlorin derivatives and a comprehensive collection of 13c data of these products and closely related compounds

Vilsmeier-formylation of the copper(II) complex of chlorin-e₆ trimethyl ester (2), under mild conditions, gives selective substitution in the 3-vinyl group. In contrast chlorination of 2 is shown to lead to selective substitution at position 20 of the macrocycle. A similar result is found for [3-ethyl]-isochlorin-e₄ dimethyl ester (17) although further reaction leads to more highly chlorinated products which have been isolated and identified. ¹³C NMR data for some of these compounds and several related chlorin derivatives are reported. In particular, after correction of the literature, many of the quaternary carbon signals of the macrocycle are assigned and substituent effects assessed. Consideration of the shifts of the α-pyrrolic carbons confirms that chlorin and its derivatives exist in a tautomeric form with the two inner H atoms on diagonally opposite pyrrole rings A and C. Such a form allows a satisfactory explanation of the substituent chemical shifts of the formyl group at positions 15 and 20 to be made.     

Solid state properties and catalytic behavior of the α- and β-vanadium bronzes

Decomposition of isopropanol (IPA) on V₂O₅, Li_0.02V₂O₅, Na_0.02V₂O₅, Na_0.06V₂O₅, Li_0.33V₂O₅, and Na_0.33V₂O₅ has been studied in the temperature range 186–300°C. The first four catalysts (α-phase) show predominately dehydration, whereas the last two (β-phase) have comparable dehydration and dehydrogenation activity. Dehydration activity increases with alkali metal concentration within the α-phase, but falls sharply on the β-phase catalysts. This difference is attributed to the different rate determining steps for the reaction on the α- and β-phase catalysts. X-ray and ir spectral data show that the β-phase catalysts are much more stable than the α-phase. A mechanism for the dehydration of IPA based on the electrical resistivity, ESR spectra, and kinetic data has been proposed.     

Nonradiative energy transfer from Tb3+ → Er3+ in calibo glass

Energy transfer studies have been made in a terbium-erbium coactivated calibo-glass system at room temperature and at liquid-air temperature. A study of the emission and decay of ⁵D₄ level of Tb³⁺ has been made by varying the acceptor (Er³⁺) concentration. Probabilities and efficiencies of energy transfer as well as donor-acceptor distances have been calculated. At low acceptor concentration the decay of the donor (Tb³⁺) emission has been found to be diffusion limited. At high acceptor concentration the mechanism governing the transfer is found to be dipole-dipole.     

Iron-57 Mössbauer effect study of the distribution of divalent and trivalent ions in potassium transition metal fluorides having the tetragonal bronze structure

Mössbauer studies are reported for compounds of the type KM^IIM^IIIF₆ (M = first-row transition metal ion, Zn, or Mg) which have the tetragonal bronze structure. The results of this investigation provide evidence that the trivalent ions are located on the 8(j) sites of the bronze structure and that the divalent ions are distributed over both the 8(j) and 2(c) sites.     

Selectivities in 1,2,3-triazolide displacements of halides and additions to alkynes

4,5-Dicarbomethoxy-1,2,3-triazolide or 4-phenyl-1,2,3-triazolide displace chloride from ethyl chloroacetate or β-chloropropionate to give both 1-N and 2-N alkylated products. Our highest 2-N to 1-N selectivity was ca 5/1 and was found with the base triethylamine in DMF. The same triazolides and others add to alkynes, e.g. ethyl propiolate, methyl acetylenedicarboxylate, phenylpropiolaldehyde, ethyl phenylpropiolate, etc, to give Michael adducts at the 2-N position exclusively. Here the usual preference holds, i.e., the anti adduct is favored, but anti to syn isomerization usually sets in. On the basis of the available data for nucleophilic substitutions and additions, a limited directioselectivity pattern emerges for H-1,2,3-triazoles (T) and their anions (T^?): neutral T almost invariably leads with 1-N; T^t-- usually adds to unsaturates at 2-N; unsubstituted, 4-substituted and 4,5-disubstituted T^? attack organic halides at both 1-N and 2-N. Compared to phenyl, 2-triazolyl exerts a greater deshielding effect on proton chemical shifts; these and other patterns in the PMR spectra of the Michael adducts are discussed. CNDO calculations indicate that the 1-H is more stable than the 2-H-1,2,3-triazole and that in both neutral triazole and in triazolide, the 1-nitrogen position should lead nucleophilic attacks-this directioselectivity prediction is only partly (and probably fortuitously) correct.