Die Reaktion von SeCl4 mit Übergangsmetalltetrachloriden. Synthese und Kristallstrukturen von (SeCl3)2MCl6 mit M = Zr,Hf, Mo,Re

The Reaction of SeCl₄ with Transition Metal Tetrachlorides. Synthesis and Crystal Structures of (SeCl₃)₂MCl₆ with M = Zr, Hf, Mo, Re The transition metal tetrachlorides ZrCl₄, HfCl₄ and MoCl₄ react with SeCl₄ in closed ampoules at temperatures of 140°C to (SeCl₃)₂MCl₆ (M = Zr, Hf, Mo) which are all isotypic and crystallize in the (SeCl₃)₂ReCl₆ structure type (orthorhombic, Fdd2, Z = 8, lattice constants for M = Zr: a = 1165.7(1)pm, b = 1287.2(2)pm, c = 2180.2(2)pm; for M = Hf: a = 1162.9(2)pm, b = 1285.0(2)pm, c = 2178.2(3)pm; for M = Mo: a = 1153.8(1)pm, b = 1267.7(1)pm, c = 2147.4(2)pm). The Cl^? ions form a hexagonal closest packing with one fourth of the octahedral holes filled by Se⁴⁺ and M⁴⁺ in an ordered way. The MCl₆ octahedra are regular, the SeCl₆ octahedra are distorted with 3 short and 3 long Se? Cl bonds (mean 215 pm and 287 pm). The structures can thus be regarded as built of SeCl₃⁺ and MCl₆^2? ions. Magnetic susceptibility measurements show for M = Zr the expected diamagnetic behavior, for M = Mo and Re paramagnetic behavior according to the Curie-Weiss law with magnetic moments of 2.5 B. M. for M = Mo and 3.7 B. M. for M = Re corresponding to 2 and 3 unpaired electrons respectivly.     

Testing the photocatalytic activity of cyanogen-and thiocyanogen-based inorganic polymers

The photocatalytic properties of some cyanogen-and thiocyanogen-based inorganic polymers, such as paracyanogens containing different metals (Hg, Ag, Cu), polythiocyanogens of different iodine contents, polycyanogen and poly (cyanogenthiocyanate), have been tested in two systems. Cu-containing paracyanogen and the iodine-poor polythiocyanogens catalyze the photoreduction of methylviologen under visible light, furthermore the Cu-containing paracyanogen catalyzes the photoreduction of water to hydrogen under UV irradiation.

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, , , , (Hg, Ag, Cu), , (), . , , , , , , -.

     

Studies on ABX6 Compounds. II. The BaThBr6 structure type

The compounds AThBr₆ (A: Ca, Sr, Ba) crystallize in an ordered substitution variant of the PuBr₃ type. Their syntheses and special features of the crystal structures are described.     

Observation of daunomycin and nogalamycin complexes with duplex DNA using electrospray ionisation mass spectrometry

The noncovalent binding of the antitumour drugs daunomycin and nogalamycin to duplex DNA has been studied using electrospray ionisation mass spectrometry (ESI-MS). The conditions for the preparation of drug/duplex DNA complexes and for their detection by ESI-MS have been optimised. Ions corresponding to these complexes were most abundant relative to free DNA when prepared in the pH range 8-9, and using gentle ESI interface conditions. Self-complementary oligonucleotides, 5'-d(GGCTAGCC)-3' or 5'-d(CGGCGCCG)-3', annealed in the presence of a 5-fold molar excess of either nogalamycin or daunomycin gave ESI mass spectra in which the most intense ions corresponded to three molecules of drug bound to duplex DNA, with some evidence for four drug molecules bound. For binding to 5'-d(TGAGCTAGCTCA)(2)-3', complexes containing up to four nogalamycin and six daunomycin molecules were observed. These data are consistent with the neighbour exclusion principle whereby intercalation occurs between every other base pair such that up to four bound drugs would be expected for the 8 mers and up to six for the 12 mer. Competition experiments involving a single drug in an equimolar mixture of two oligonucleotides (5'-d(TGAGCTAGCTCA)(2)-3' with either 5'-d(CGGCGCCG)(2)-3' or 5'-d(GGCTAGCC)(2)-3') showed ions arising from complexes of drug/5'-d(CGGCGCCG)(2)-3' were more intense than complexes of drug/5'-d(GGCTAGCC)(2)-3', relative to those from the 12 mer in each mixture. While this suggests ESI-MS has the potential to detect differences in sequence selectivity, more detailed experiments involving a comparison of the relative ionisation efficiency of different oligonucleotides and a wider range of intercalators are required to establish this definitively. ESI mass spectra from experiments in which both drugs were reacted with the same oligonucleotide were more complex, such that a clear preference for one drug could not be established.     

Mikrochemischer Nachweis von Europium in Gemischen seltener Erden

Zusammenfassung Zweiwertige Europiumsalze reduzieren Kakothelin zu einem violetten Farbstoff, analog wie die niederen Oxydationsstufen von Titan, Zinn, Vanadin, Niob, Molybdän, Wolfram, Uran und Rhenium. Man kann diese Reaktion zum spezifischen Nachweis von Europium in Gemischen seltener Erden benutzen. Die Erfassungsgrenze des Europiumnachweises beträgt 3/ccm, wenn man die Reduktion mit Zink und Salzsäure in Gegenwart von Kakothelin durchführt.

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Summary Bivalent europium salts, in analogy with the low oxidation steps of titanium, tin, vanadium, columbium, molybdene, tungsten, uranium, and rhenium, reduce cacotheline to a violet dyestuff. This reaction can be used for the specific detection of europium in mixtures of rare earths. The limit of identification of this test for europium is 3/ccm. if the reduction is carried out with the help of zinc and hydrochloric acid in the presence of cacotheline.

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Résumé Les sels d'europium bivalents réduisent la cacothéline à un principe colorant violet, de même que les premiers degrés d'oxydation du titane, de l'étain, du vanadium, du niobium, du molybdène, du tungstène, de l'urane et du rhénium. On peut employer cette réaction pour l'identification de l'europium dans un mélange de terres rares. On peut déceler 3 d'europium dans 1 ccm., si la réduction est produite par l'addition du zinc et de l'acide chlorhydrique, en présence de cacothéline.

     

Effect of metal ions forming bromide complexes on the Belousov-Zhabotinskii reaction

Metal ions forming stable complexes with bromide ions greatly influence both the amplitude and frequency of the Belousov-Zhabotinskii reaction. In case of thallium(I), redox reactions involving the metal ion should also be considered beside complex formation.

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, , , -. (I), , .

     

Pseudohalogeno-Metallverbindungen. LXXV. Pentacarbonylrhenium-und Triphenylphosphangold-Komplexe mit Pseudohalogeniden: (OC)5ReX,Ph3PAuX (X = ONC(CN)2, o-MeC6H4SO2C(CN)2,o-MeC6H4SO2NCN,Ph2(S)PNCN)

Pseudohalogeno Metal Compounds. LXXV. Pentacarbonylrhenium and Triphenylphosphinegold Complexes of Pseudohalide Anions: (OC)₅ReX, Ph₃PAuX (x = ONC(CN)₂, o-MeC₆H₄SO₂C(CN)₂, o-MeC₆H₄SO₂NCN, Ph₂(S)PNCN) The pseudohalides (X^?) nitrosodicyanmethanide, o-tosyldicyanmethanide, o-tosylcyanamide and diphenylthiophosphinylcyanamide react with the Organometallic Lewis Acids (OC)₅Re⁺ (as (OC)₅ReFBF₃) and Ph₃PAu⁺ (as Ph₃PAuNO₃) to give the neutral title complexes (OC)₅Re—X and Ph₃PAu? X, respectively. X-ray diffraction shows that nitroso-dicyanmethanide is coordinated through the nitroso N-atom to the Re(CO)₅ fragment. Cyanide-N-coordination is observed for the complexes with o-tosyldicyanmethanide and o-tosylcyanamide whereas diphenylthiophosphinylcyanamide is S-coordinated to the gold atom. Spectroscopic data (IR, NMR) of 1–6 are described.     

“Integer-making” theorems

Let X = {x₁, x₂,…} be a finite set and associate to every x_i a real number α_i. Let f(n) [g (n)] be the least value such that given any family $\text{F}$ of subsets of X having maximum degree n [cardinality n], one can find integers α_i, i=1,2,… so that α_i ? α_i|<1 and

$\text{∑}\text{x}{}_{\mathrm{i\; ?\; E}}\text{a}{}_{\mathrm{i}}\text{?}\text{∑}\text{x}{}_{\mathrm{i\; ?\; E}}\text{α}{}_{\mathrm{i}}\text{≤?(n)}\text{∑}\text{x}{}_{\mathrm{i\; ?\; E}}\text{a}{}_{\mathrm{i}}\text{?}\text{∑}\text{x}{}_{\mathrm{i\; ?\; E}}\text{α}{}_{\mathrm{i}}\text{≤}\text{g(n)}$

for all $\text{E ?}\text{F}$. We prove

$\text{f(n)≤n ? 1 and g(n)≤c(n}\text{log}\text{n)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$

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A study of methods for moving particles in RF processing plasmas

Methods for moving charged particles in RF processing plasmas are investigated. These methods include varying RF power, varying chamber pressure, attraction and repulsion by an electrostatic probe, and movement with magnetic fields. Varying RF power changes the depth of the potential wells where particles are trapped. The RF power affects shape and location of the traps and the bulk plasma potential. Increasing the chamber pressure moves the sheath edge closer to the wafer being processed. Since particle traps are found at the plasma sheath edge increasing the chamber pressure will move the particle traps (and any trapped particles) closer to the wafer being processed. The Langmuir probe can repel particles when under negative bias and attract them when positively biased. This probe can also distort the sheath edge when the tip resides within the sheath. Applying a magnetic field can change the characteristics of the particle traps and produce a force on the charged dust particles