ZnTe6O13, a new ZnO–TeO2 phase

Our investigations into the ZnO–TeO₂ system have produced a new phase, zinc(II) hexatellurium(IV) tridecaoxide, ZnTe₆O₁₃, with trigonal (R) symmetry, synthesized by repeated heating and cooling to a maximum temperature of 1053 K. The asymmetric unit consists of a Zn atom coordinated in a distorted octahedral fashion by two unique tellurium(IV) oxide units that form trigonal–bipyramidal TeO₄ and TeO₃₊₁ corner‐ and edge‐shared polyhedra. Except for the Zn and an O atom, which occupy 6c positions, all atoms occupy 18f general positions.     

The asymptotic numbers of regular tournaments,Eulerian digraphs and Eulerian oriented graphs

LetRT(n), ED(n) andEOG(n) be the number of labelled regular tournaments, labelled loop-free simple Eulerian digraphs, and labelled Eulerian oriented simple graphs, respectively, onn vertices. Then, asn,, for any>0. The last two families of graphs are also enumerated by their numbers of edges. The proofs use the saddle point method applied to appropriaten-dimensional integrals.     

Aerobic oxidation of methyl p-tolyl sulfide catalyzed by a remarkably labile heteroscorpionate RuII-aqua complex,fac-[RuII(H2O)(dpp)(tppm)]2+

fac-[RuII(Cl)(dpp)(L3)]+ (L3 = tris(pyrid-2-yl)methoxymethane (tpmm) = [1A]+ and tris(pyrid-2-yl)pentoxymethane (tppm) = [1B]+ and dpp = di(pyrazol-1-yl)propane) rapidly undergo ligand substitution with water to form fac-[RuII(H2O)(dpp)(L3)]2+ (L3 = tpmm = [2A]2+ and tppm = [2B]2+). In the structure of [2A]2+, the distorted octahedral arrangement of ligands around Ru is evident by a long Ru(1)-O(40) of 2.172(3) A and a large angle O(40)-Ru(1)-N(51) of 96.95(14) degrees . The remarkably short distance between O(40) of H2O and H(45a) of dpp confirms the heteroscorpionate ligand effect of dpp on H2O. [2B]2+ aerobically catalyzes methyl p-tolyl sulfide to methyl p-tolyl sulfoxide in 1,2-dichlorobenzene at 25.0 +/- 0.1 degrees C under 11.4 psi of O2. Experimental facts in support of this aerobic sulfide oxidation are the absence of H2O2 and the oxidative reactivity of the putative Ru(IV)-oxo intermediate toward methyl p-tolyl sulfide, 2-propanol, and allyl alcohol. This study provides the first documented example of aerobic-sulfide oxidation catalyzed by the remarkably labile heteroscorpionate Ru(II)-aqua complex without the formation of a highly reactive peroxide as an intermediate.     

Lanthanide distribution in some doped alkaline earth aluminates and gallates

High-resolution neutron and synchrotron X-ray powder diffraction studies are reported for the six oxides AB₂O₄ (A=Ca²⁺, Sr²⁺ and Ba²⁺ and B=Al³⁺ and Ga³⁺). These oxides all adopt a stuffed tridymite type structure, the precise nature of which depends on both the A- and B-type cations. Bond valence calculations reveal a range of values for the various A-type cations, in all cases at least one site is significantly underbonded. Conversely the tetrahedral B-type sites invariably exhibit unexceptional bond valencies. Attempts to dope the oxides with various lanthanides to the 1% level invariably resulted in some segregation into alternate phases located at the grain boundaries. The identity of the impurity phases is presented and the importance of bond valencies in understanding this segregation is highlighted.     

Intermolecular Domino Reaction of Two Aryl Iodides Involving Two C?H Functionalizations

A palladium‐catalyzed intermolecular cross‐coupling of two aryl iodides is reported, giving polycyclic ring systems with a high level of convergence and efficiency.