The reactions of tellurium tetrahalides with triphenylphosphine under ambient conditions

The reactions of tellurium tetrahalides and triphenylphosphine in tetrahydrofuran have been carried out under ambient conditions and afford [(Ph(3)PO)(2)H](2)[Te(2)X(10)] [X = Cl (1), Br (2)] and [(Ph(3)PO)(3)(OH(3)])(2)[TeI(6)] (4). The X-ray structures of 1 and 2 show that they are isostructural and contain discrete [Te(2)X(10)](2-) anions exhibiting octahedral coordination around both tellurium atoms with one shared edge and [Ph(3)POH...OPPh(3)](+) cations that show strong hydrogen bonds (the O...O distances are 2.399 and 2.404 A for 1 and 2, respectively). The compound 4 is built up with discrete octahedral hexaiodotellurate anions and [(Ph(3)PO)(3)(OH(3))](+) cations. The reaction of TeBr(4) and PPh(3) also results in the formation of formally zwitterionic Ph(3)PO(CH(2))(4)TeBr(4) (3). This reaction involves an unprecedented THF ring opening in which the oxygen atom becomes bonded to the phosphorus atom of triphenylphosphine and the carbon atom at the other end of the five-atomic chain becomes bonded to the tellurium atom of TeBr(4). The ring opening of the solvent THF is also taking place in the reaction involving tellurium tetraiodide, as indicated by the formation of C(4)H(8)TeI(2) (5). The reaction may initially lead to Ph(3)PI(2) that reacts with THF yielding Ph(3)PO and ICH(2)(CH(2))(2)CH(2)I. The latter species reacts with elemental tellurium producing 5. Depending on the conditions upon crystallization, two polymorphs of C(4)H(8)TeI(2) (5a and 5b) are observed. While the molecular structures of the two forms are virtually identical, their packing and intermolecular contacts are different. Two further minor products (6a and 6b) were isolated in the reaction of TeI(4) and PPh(3): Both are formally 1:1 adducts of 5 and TeI(4), but they differ considerably in their structures. 6a can be formulated as [C(4)H(8)TeI(+)](2)[Te(2)I(10)(2-)] and 6b as [C(4)H(8)TeI(+)](2)(TeI(3)(+))(2)(I(-))(4). The latter compound exhibits framework similar to that of the tetramers in gamma- and delta-TeI(4).     

Genes encoding enzymes responsible for biosynthesis of L-lyxose and attachment of eurekanate during avilamycin biosynthesis

The oligosaccharide antibiotic avilamycin A is composed of a polyketide-derived dichloroisoeverninic acid moiety attached to a heptasaccharide chain consisting of six hexoses and one unusual pentose moiety. We describe the generation of mutant strains of the avilamycin producer defective in different sugar biosynthetic genes. Inactivation of two genes (aviD and aviE2) resulted in the breakdown of the avilamycin biosynthesis. In contrast, avilamycin production was not influenced in an aviP mutant. Inactivation of aviGT4 resulted in a mutant that accumulated a novel avilamycin derivative lacking the terminal eurekanate residue. Finally, AviE2 was expressed in Escherichia coli and the gene product was characterized biochemically. AviE2 was shown to convert UDP-D-glucuronic acid to UDP-D-xylose, indicating that the pentose residue of avilamycin A is derived from D-glucose and not from D-ribose. Here we report a UDP-D-glucuronic acid decarboxylase in actinomycetes.     

In situ reaction mechanism studies on the atomic layer deposition of Al2O3 from (CH3)2AlCl and water

Reaction mechanisms between dimethylaluminum chloride and deuterated water in the atomic layer deposition (ALD) of Al2O3 were studied at 150-400 degrees C using a quartz crystal microbalance (QCM) and a quadrupole mass spectrometer (QMS). The observed reaction byproducts were DCl and CH3D. QMS showed that about one-third of the chlorine, and half of the methyl ligands were released during the (CH3)2AlCl pulse. The growth rate deduced from the QMS and QCM data was in qualitative agreement with the previously published growth rate from ALD film growth experiments.     

Linear Clique‐Width for Hereditary Classes of Cographs

The class of cographs is known to have unbounded linear clique‐width. We prove that a hereditary class of cographs has bounded linear clique‐width if and only if it does not contain all quasi‐threshold graphs or their complements. The proof borrows ideas from the enumeration of permutation classes.     

Cobalt complexes of a selenium diimide and a tellurium diimide dimer

[CoCl₂{N,N′-Te₂(N^tBu)₄}] (1) was obtained in good yields by the reaction of equimolar amounts of (^tBu)NTe(μ-N^tBu)₂TeN(^tBu) and CoCl₂ in toluene under an argon atmosphere. The crystal structure of 1·CH₂Cl₂ showed that the dimeric tellurium diimide ligand is N,N′-chelated to cobalt. The related reaction of Se(N^tBu)₂ and CoCl₂ affords a green product tentatively identified as a 1:1 adduct [CoCl₂{N,N′-Se(N^tBu)₂}] (CHN analysis). However, recrystallization from thf produces the ion-separated complex [Co₂(μ-Cl)₃{N,N′-Se(N^tBu)₂}₂(thf)₂][CoCl₃{NH₂(^tBu)}]·1½thf (2·1½thf), in which the monomeric selenium diimide ligand is N,N′-chelated to cobalt in the cation. A pathway for the formation of 2 from [CoCl₂{N,N′-Se(N^tBu)₂}] in thf is proposed.     

1,3,5,7‐Tetraselena‐2,4,6,8(2,5)‐tetrathiophenaoctaphane

The novel title tetraselenacalix[4]arene, C₁₆H₈S₄Se₄ or [(C₄H₂S)Se]₄, has a centrosymmetric cyclic molecular structure with approximate C_2h molecular symmetry. The four thienyl rings are joined together by Se bridges and exhibit a syn–syn–anti–anti arrangement around the mol­ecule. The lattice consists of skewed stacks of mol­ecules, with chalcogen–chalcogen close contacts binding the stacks together, forming a two‐dimensional network of mol­ecules.     

A Selenium‐Nitrogen Chain with Selenium in Different Oxidation States

The reaction of tBuNH₂ with a mixture of SeCl₂ and SeOCl₂ in a 6:2:1 molar ratio produces the novel selenium‐nitrogen chain ClSeN(tBu)Se(O)Cl ( 4 ), in which the selenium atoms are in two different oxidation states, Se^II and Se^IV. The crystal structure of 4 is compared with that of the related Se^II/Se^II system ClSeN(tBu)SeCl ( 1 ) and differences are attributed to hyperconjugative effects. The energetics of the formation of 4 via two different routes are elucidated by PBE0/def2‐TZVPP calculations.     

Characterization of a total diet reference material (ARC/CL HDP) for contents of essential and toxic elements

Summary A total diet reference material (RM) was prepared by employing material leftover from a nationwide Finnish hospital diet study. The material was carefully homogenized using Ti-blades, freeze-dried, rehomogenized with Ti-blades, passed through a 2 mm nylon sieve and carefully mixed in large glass cylinders. Homogeneity of the material divided into 20 g samples in polyethylene bottles was tested by taking ten 0.5 g samples from the beginning and end of the bottling line and analyzing them for Zn and Mg. The homogeneity was within 1.0% for both Zn and Mg. An interlaboratory comparison study involving reliable reference laboratories that employed a total of seven methods based on independent analytical principles was conducted on the contents of 14 mineral elements. After the exclusion of outliers the recommended concentrations (on a dry weight basis) expressed as the medians±95% confidence limits were established as follows: Ca=2.86±0.124 mg/g, Mg=785±25 g/g, K=9.42±0.30 mg/g, Na=7.87±0.57 mg/g, Fe=30.4±0.9 g/g, Mn=12.9±0.58 g/g, Zn=28.9±1.3 g/g, Cu=3.18±0.19 g/g, Mo=262±35 ng/g, Ni=271±38 ng/g, Se=181±17 ng/g, Pb=43±8 ng/g, Cd=21±3 ng/g and Hg=6.6±3.6 ng/g. All of the above recommended concentration ranges, except that for Ni, fell into category A, i.e. values recommended with a high degree of confidence according to the certification criteria established by Pszonicki.     

Formation and structural characterization of novel polynuclear palladium selenolato complexes [Pd3Se(SePh)3(PPh3)3]Cl and [Pd6Cl2Se4(SePh)2(PPh3)6]

In addition to well-known dinuclear phenylselenolato palladium complexes, the reaction of [PdCl₂(PPh₃)₂] and NaSePh affords small amounts of novel trinuclear and hexanuclear complexes [Pd₃Se(SePh)₃(PPh₃)₃]Cl (1) and [Pd₆Cl₂Se₄(SePh)₂(PPh₃)₆] (2). Complex 1 is triclinic, P1?, a=13.6310(2), b=16.2596(2), c=16.9899(3) Å, α=83.1738(5), β=78.9882(5), γ=78.7635(5)°. Complex 2 is monoclinic, C2/c, a=25.7165(9), b=17.6426(8), c=27.9151(14) Å, β=110.513(2)°. There are no structural forerunners for 1, but the hexanuclear complex 2 is isostructural with [Pd₆Cl₂Te₄(TeR)₂(PPh₃)₆] (R=Ph, C₄H₃S) that have been observed as one of the products in the oxidative addition of R₂Te₂ to [Pd(PPh₃)₄]. Mononuclear palladium complexes may play a significant role as building blocks in the formation of the polynuclear complexes.     

Split Permutation Graphs

The class of split permutation graphs is the intersection of two important classes, the split graphs and permutation graphs. It also contains an important subclass, the threshold graphs. The class of threshold graphs enjoys many nice properties. In particular, these graphs have bounded clique-width and they are well-quasi-ordered by the induced subgraph relation. It is known that neither of these two properties is extendable to split graphs or to permutation graphs. In the present paper, we study the question of extendability of these two properties to split permutation graphs. We answer this question negatively with respect to both properties. Moreover, we conjecture that with respect to both of them the split permutation graphs constitute a critical class.