Die Kristallstruktur von Ge5O[PO4]6

Zusammenfassung Die Kristallstruktur der Verbindung Ge₅O[PO₄]₆ wurde auf Grund dreidimensionaler Einkristalldaten ausWeissenberg-Aufnahmen ermittelt und nach der Methode der kleinsten Quadrate verfeinert: Raumgruppe ;a=7,994±0,004 undc=24,87±0,01 Å;Z=3; 467 unabhängige Reflexe;R=0,086.Die Kristallstruktur wird aus singulären [GeO₆]-Oktaedern und [Ge₂O₇]-Doppeltetraedern aufgebaut, die über [PO₄]-Tetraeder zu einem dreidimensionalen Strukturverband vernetzt sind. Die mittleren Abstände betragen: Ge^[6]–O=1,863, Ge^[4]–O=1,704 und P–O=1,525 Å.

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The crystal structure of Ge₅O[PO₄]₆

The crystal structure of Ge₅O[PO₄]₆ has been determined and refined by least-squares, using three-dimensional x-ray data fromWeissenberg-photographs: space group ;a=7.994±0.004 andc=24.87±0.01 Å;Z=3; 467 independent reflections;R=0.086.The crystal structure consists of isolated [GeO₆] octahedra and [Ge₂O₇] double tetrahedra which are linked by [PO₄] groups forming a three-dimensional network. The average interatomic distances are: Ge^[6]–O=1.863, Ge^[4]–O=1.704 and P–O=1.525 Å.

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Mit 2 Abbildungen     

FTIR-spectroscopy as a highly sensitive technique to study adsorption and desorption on ionic film and single crystal surfaces

Sample/spectrum relationships are investigated using both a low resolution rapid-scanning NIR monochromator and a Fourier transform instrument capable of high resolution and are evaluated in terms of whether or not the resolution of the instrument is sufficient for measuring the natural bandwidths corresponding to the sample. Based on the sample/spectrum relationship a criterion is developed which must be followed in order to apply either derivative spectroscopy or deconvolution to enhance the resolution of overlapped bands without generating spectral artifacts.     

Gas-phase derivatization of [C3H5]+ ions using tandem mass spectrometry methods A13C labelling study

The study of specifically ¹³C-labelled precursors sheds further light on the gas-phase chemistry of allyl and 2-propenyl cations. It is demonstrated that both species are formed from allyl and 2-propenyl bromide upon 70 eV electron impact ionization without skeletal reorganization. Gas-phase derivatization of the [C₃ H₅]⁺ ions with benzene facilitates, as suggested and observed earlier, the distinction of the two isomers using collision-induced dissociation of the Wheland complexes (or isomers thereof). The ¹³C labelling data clearly demonstrate that 64% of allyl cations survive the derivatization while 36% isomerize to 2-phenylpropyl cations; the latter are also formed via the reaction of 2-propenyl cation with benzene, protonation of α-methylstyrene and water loss from protonated 2-phenyl-2-propanol, respectively. Unimolecular loss of C₂H₄ from protonated allylbenzene proceeds via two competing reaction channels: one involves heterolysis of 1-phenylpropyl cations (～30%); the major pathway (～70%), however, involves decomposition via propylene benzenium ions.     

1-Alkoxy-2-azaallenyl-komplexe von chrom und wolfram

The successive reaction of (CO)₆M with Na[NCR₂¹] and [Et₃O]BF₄ yields (CO)₅M[C(NCR₂¹)OEt] (II: M = Cr; III: M = W; CR₂¹ = C(C₆H₄Br-p)₂ (a), CPh₂ (b), C(C₆H₄OMe-p)₂ (c), C(C₆H₄)₂O (d), CBu₂^tt (e)). Hexacarbonyltungsten, (CO)₆W, reacts with Na[NCPh₂] and MeOSO₂F to give (CO)₅W[C(NCPh₂) OMe] (IV). X-Ray analysis of IIe shows that: (1) the CNC fragment is almost linear (171.7°); (2) the two NC bond lengths are equal within experimental error; and (3) the O,C,Cr,N plane is perpendicular to the C(Me₃),C,N,C(Me₃) plane (90.0°). Therefore compounds II–IV are best described as 1-alkoxy-2-azaallenyl complexes.     

Darstellung und Eigenschaften von Chromtricarbonyl-Komplexen strukturisomerer Borazin-Derivate

The new hexaalkylborazine chromium tricarbonyls (n-Pr)₃B₃N₃Me₃Cr(CO)₃ (V), Me₃B₃N₃(n-Pr)₃Cr(CO)₃ (VI), (i-Pr)₃B₃N₃Me₃Cr(CO)₃ (VII) and Me₃B₃N₃(i-Pr)₃Cr(CO)₃ (VIII) have been prepared from fac-Cr(CO)₃(MeCN)₃ and the corresponding borazine in dioxane or without solvent. They are much more labile than the isomeric complex Et₃B₃N₃Et₃Cr(CO)₃ (IV) which can be readily obtained from Et₃B₃N₃Me₃Cr(CO)₃ and Et₃B₃N₃Et₃ by ring ligand exchange. The NMR., IR., UV. and Mass spectroscopic data of the complexes IV–VIII will be briefly discussed. The preparation of the borazine derivatives (n-Pr)₃B₃N₃Me₃ (IX) and Me₃B₃N₃(n-Pr)₃ (X) is also reported.     

Liquid crystalline ionomers. II. Main chain liquid crystalline polymers with terminal sulfonate groups

Liquid crystalline ionomers containing sulfonate groups on the terminal unit of the chain were synthesized by an interfacial condensation reaction of 4,4′-dihydroxy-α,α′-dimethyl benzalazine, the monofunctional dye fast yellow (FY), and a 50/50 mixture of sebacoyl and dodecanedioyl dichlorides. The weight-average molecular weights were estimated from inherent viscosity measurements to be between 6000–11,000 and the sodium sulfonate concentrations ranged from 0–18.4 meq/100 g polymer. Elemental analyses, however, indicated much higher molecular weights, which suggested that there was a distribution of chains with one, two, or no FY endgroups. The polymers were semicrystalline and melted at ca. 140°C to form nematic mesophases that were stable over a temperature range of ca. 80°C. They were thermally stable to about 350°C. The ionomeric nature of the polymers was confirmed by the presence of intermolecular associations in nonpolar solvents, as demonstrated by dilute solution viscosity measurements.     

SINGLE- and DOUBLE-STRAND BREAK FORMATION IN DOUBLE-STRANDED DNA UPON NANOSECOND LASER-INDUCED PHOTOIONIZATION

Double-stranded (ds) calf thymus DNA (0.4 mM), excited by 20 ns laser pulses at 248 nm, was studied in deoxygenated aqueous solution at room temperature and pH 6.7 in the presence of a sodium salt (10 mM). The quantum yields for the formation of hydrated electrons (phi c-), single-strand breaks (phi ssb) and double-strand breaks (phi dsb) were determined for various laser pulse intensities (IL). phi c- and phi ssb increase linearly with increasing IL; however, phi ssb has a tendency to reach saturation at high IL (greater than 5 X 10(6) Wcm-2). The ratio phi ssb/phi c-, representing the number of ssb per radical cation, is about 0.08 at IL less than or equal to 5 X 10(6) Wcm-2. For comparison, the number of ssb per OH radical reacting with dsDNA is 0.22. On going from argon to N2O saturation, phi ssb and phi dsb become larger by factors of approximately 5 and 10-15, respectively. This enhancement is produced by attack on DNA bases by OH radicals generated by N2O-scavenging of the photoelectrons. While phi ssb is essentially independent of the dose (Etot), phi dsb depends linearly on Etot in both argon- and N2O-saturated solutions. The linear dependence of phi dsb implies a square dependence of the number of dsb on Etot. This portion of dsb formation is explained by the occurrence of two random ssb, generated within a critical distance (h) in opposite strands. For both argon- and N2O-saturated solutions h was found to be of the order of 40-70 phosphoric acid diester bonds. On addition of electron scavengers such as 2-chloroethanol (or N2O plus t-butanol), phi dsb is similar to that in neat, argon-saturated solutions. Thus, hydrated electrons are not involved in the chemical pathway leading to laser-pulse-induced dsb of DNA.     

Transport efficiency in femtosecond laser ablation inductively coupled plasma mass spectrometry applying ablation cells with short and long washout times

Relative mass transport efficiencies of near infrared (λ = 795 nm) femtosecond laser generated brass aerosols in helium were measured by ICP-MS applying different ablation cells with short and long washout times. It was found that the transport efficiencies are independent of the cell used within the mutual experimental uncertainties. This finding was confirmed by additional measurements providing the absolute particle mass transport efficiencies of femtosecond laser ablation in He. Here, the transport efficiencies were determined by weighing the samples before and after ablation with a micro-balance, collecting the particles by low-pressure impaction, and evaluating the impacted masses quantitatively by total reflection X-ray fluorescence. Within the experimental uncertainties (± 9–19%) the same absolute transport efficiency (about 77%) was found for all cells applied. This efficiency value can be regarded as a lower limit of the absolute mass transport efficiency since mass losses in the impactor are difficult to quantify.     

Organische Schwefelverbindungen—IV: Elektronenstossinduzierte Redoxreaktion von ortho-Nitrothiobenzoesäure-S-p-tolylester

The electron-impact fragmentation of S-p-tolylester of nitrothiobenzoic acid leads to a previously unknown rearrangement in the case of the ortho compound. This consists of an intra molecular redoxreaction with oxygen transfer from the o-nitro group onto the sulphur of the thiol ester group. The position of the nitro group is not only an essential influence on the fragmentation pattern, but also of dramatic importance in determining the lifetime of the molecular ion.     

Ferromagnetism in a dinuclear nickel(II) complex containing triethylenetetramine and tricyanomethanide

Triethylenetetramine (L(4)) was used as a tetradentate blocking ligand that, after complexation with Ni(II), leaves two sites ready for ligation with tricyanomethanide. The formed binuclear complex [L(4)Ni(NCC(CN)CN)(2)NiL(4)](ClO(4))(2) exhibits a ferromagnetic coupling with J/hc = +0.15 cm(-1) and g(Ni) = 2.126; below 16 K, a ferromagnetic ordering is evidenced by ac magnetic susceptibility (both in-phase and out-of-phase), magnetization, field-cooled magnetization, and zero-field-cooled magnetization measurements.