Rational Synthesis of Molybdenum(V) Tetramers Consisting of [Mo2O4]2+ Dimers Held Together by Bridging Phosphinate Ligands and the Tungsten(VI) Dimer [(CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2]: Structural and Theoretical Considerations

Reacting MoO₂(acac)₂ with Ph₂POOH or Me₂POOH in EtOH results in the formation of the tetranuclear molybdenum (V) clusters Mo₄(μ ₃-O)₄(μ-O₂PR₂)₄O₄, PR₂ = PPh₂, 1, or PMe₂, 2, in functional yields (>90% and 55% respectively). The reaction of WO₂(acac)₂ with Ph₂POOH in MeOH affords the tungsten dimer [(CH₃O)₂(O)W(μ-O)(μ-O₂PPh₂)₂W(O)(CH₃O)₂], 3. The single crystal X-ray determined structures of complexes 1–3 are reported. In 1 and 2, the four Mo=O units are interconnected by four triply bridging oxygen atoms, resulting in a distorted cubic-like structure for the Mo₄(μ ₃-O)₄O₄ units. Each molybdenum atom forms two additional Mo–O bonds with two oxygen atoms from different adjacent phosphinato ligands. Complex 3, a tungsten dimer, contains packing disorder and consists of bridging oxo and diphenylphosphinato ligands. The bonding of 1 and 2 assessed by density-functional methods showed that bonding between the Mo(V) centers occurs through σ overlap of the d _xy orbitals. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. Dedicated to the memory of Professor F. A. Cotton. Veritas numquam perit.     

Dynamic Frequency Shifts of Complexed Ligands: An NMR Study ofd-[1-C,1-H]Glucose Complexed to theEscherichia coliPeriplasmic Glucose/Galactose Receptor

The¹³C multiplet structure ofd-[1-¹³C,1-²H]glucose complexed to theEscherichia coliperiplasmic glucose/galactose receptor has been studied as a function of temperature. Asymmetric multiplet patterns observed are shown to arise from dynamic frequency shifts. Multiplet asymmetry contributions resulting from shift anisotropy–dipolar cross correlations were found to be small, with optimal fits of the data corresponding to small, negative values of the correlation factor, χ^CD-CSA. Additional broadening at higher temperatures most probably results from ligand exchange between free and complexed states. Effects of internal motion are also considered theoretically, and indicate that the order parameter for the bound glucose is ≥0.9.     

An automated fluorescence assay for dissolved total amino acids from marine waters in the presence of interfering material

Summary For the determination of dissolved total amino acids from seawater a method is recommended that was based on the fluorimetric detection of primary amines with o-phthaldialdehyde (OPA). Automatic measurements are performed and calibrated with an amino acid mixture standard. Proteins which interfere with the procedure are separated by gel filtration. Ammonia which is also detected by OPA has to be determined additionally and corrected. The fluorescent response is linear over a wide range. The detection limit is in femtomol concentrations.

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Automatische fluorimetrische Bestimmung von gelösten Gesamt-Aminosäuren in Meerwasser in Gegenwart von störenden Substanzen

Zusammenfassung Für die Bestimmung von im Meerwasser gelösten Gesamt-Aminosäuren wird eine Methode empfohlen, die auf einem fluorimetrischen Nachweis primärer Amine mit o-Phthaldialdehyd (OPA) basiert. Die Messungen erfolgen automatisch und werden gegen ein Aminosäurengemisch als Standard geeicht. Proteine, die den Nachweis stören, werden durch Gelfiltration abgetrennt. Ammonium, das ebenfalls durch OPA angezeigt wird, muß separat gemessen und korrigiert werden. Das Fluoreszenz-Signal ist über einen weiten Bereich linear. Die untere Nachweisgrenze liegt im Femtomolbereich.

     

Computer aided mathematical analysis of interferences in spark source mass spectrometry spectra

Summary When analysing sulphide ores by spark source mass spectrometry different interferences on some mass-to-charge ratios, such as 60–62 (Ni) and 193–197 (Ir,Pt,Au), have been observed. These lines should be used in the estimation of element concentrations. Our program (SM13) gives hints to possible molecular ions derived from the matrix of the sample by using the theory of combination.The validity of this theory was checked by analysing the ASK III standard [3] and mixtures of sulphides and oxides. The formation of interfering molecular ions such as SiS⁺ and AgFeS⁺ was checked.

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Computergestützte mathematische Auswertung von Interferenzen in Funken-Massenspektren

Zusammenfassung Bei der Analyse sulfidischer Erze wurden in der Funken-Massenspektrometrie für die Masse-zu-Ladungs-Verhältnisse 60–62 (Ni) sowie 193–197 (Ir,Pt,Au), die für die Elementbestimmungen verwendet werden sollten, Interferenzen beobachtet. Hierzu wurden mit Hilfe eines Auswertungsprogramms (SM13) durch mathematische Kombinatorik Hinweise auf Interferenzen durch mögliche Molekülionen aus der Matrixzusammensetzung abgeleitet.Die Anwendbarkeit des mathematischen Modells wurde am ASK III Standard [3] sowie an Mischungen von Sulfiden und Oxiden erprobt. Die Bildung der interferierenden Molekülionen des Typs SiS⁺ und AgFeS⁺ konnte nachgewiesen werden.

     

Syntheses and structures of three complexes of formulas [L3Co(μ2-O2P(Bn)2)3CoL'][L"], featuring octahedral and tetrahedral cobalt(II) geometries; variable-temperature magnetic susceptibility measurement and analysis on [(py)3Co(μ2-O2PBn2)3Co(py)][ClO4

The syntheses and structural properties of three dinuclear complexes [L(3)Co(μ(2)-O(2)P(Bn)(2))(3)CoL'][L"] [one ionic L(3) = py(3), L' = py, L" = ClO(4)(-) (1) and two molecular L(3) = py(3), L' = Cl (2) and L(3) = py, μ(2)-NO(3)(-), L' = py (3)] are reported. Complexes feature octahedral Co(II) sites bridged by three dibenzylphosphinate ligands to a tetrahedrally ligated Co(II) site, with the remaining coordination sites occupied by py, nitrato, and Cl ligands. The Co-Co distances are 4.248 ? at 291 K and 4.265 ? at 100 K for 1 and 4.278 and 4.0313(7) ? for 2 and 3, respectively at 100 K. A fit of the low-temperature magnetic susceptibility data was derived for complex 1 with g = 2.25, TIP = 700 × 10(-6) cm(3) mol (-1), λ = -173 cm(-1), κ = 0.93, ν = -3.9, Δ = 630 cm(-1), J = 0.15 cm(-1), and θ = -1.8 resulting in R(χ(M)) = 2.5 × 10(-5) and R(χ(M)T) = 5.8 × 10(-5).     

Construction of a three-dimensional network with open channels via Ag–Ag and π–π interactions between nanoscale sized molecular chains

The reaction of Ag₂O with pybz (pybz=4-(4-pyridyl)benzoate) gave the monomer compound [Ag(pycz)(H₂O)], 1. Using 4,4′-bipyridyl (bpy) as a spacer to increase the length of the monomer resulted in the nanosized molecular chain compound [Ag₂(pybz)₂(bpy)], 2. In 1, two monomers [Ag(pycz)(H₂O)] are combined together through Agπ, ππ and Ag(CC) interactions to form a dimer, with the distances of 3.34, 3.56 and 3.18 Å, respectively. In 2, the [Ag₂(pybz)₂(bpy)] units are held together via ππ (3.4–3.5 Å) interactions resulting in a 3D network with 1D open channels.     

Trace element determinations in uranium bearing minerals and rocks by spark source mass spectrometry

Summary Spark source mass spectrometry has been used in the multielemental analyses in the samples: BIR, DNC, and W-2 of the U.S. Geological Survey (USGS). The concentrations for up to 23 trace elements could be determined depending on the concentration level and matrix composition. The USGS standards W-1 and BCR-1 were used as multi-elemental standards to evaluate the necessary sensitivity factors. The determinations of U and Th concentrations of DL-1a (Canada Centre for Mineral and Energy Technology, CANMET) are based on sensitivity factors of CANMET DH-1, BL-1, BL-2, BL-3, and BL-4 standard material. The agreement between our U and Th values and those concentration values supplied from CANMET at the end of the round robin program for the standardization was found to be good.The application of spark source mass spectrometry is demonstrated by determining the concentrations of 10 geochemical relevant elements in two drill cores of a uranium deposit and neighbouring rocks.

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Spurenelementbestimmungen an Uran-haltigen Mineralen und Gesteinen mittels Funken-Massenspektrometrie

Zusammenfassung Die Konzentrationen von bis zu 23 Spurenelementen wurden in den Proben BIR, DNC und W-2 des U.S. Geological Survey (USGS) mit Hilfe der Funken-Massenspektrometrie ermittelt. Die Standards W-1 und BCR-1 (USGS) wurden für die Bestimmung der erforderlichen Empfindlichkeitsfaktoren herangezogen. Zur Bestimmung der U- und Th-Konzentrationen in der zu standardisierenden DL-1a Probe des Canada Centre for Mineral and Energy Technology (CANMET) wurden die CANMET Standards DH-1, BL-1, BL-2, BL-3 und BL-4 für die Ermittlung der Empfindlichkeitsfaktoren benutzt. Die Meßergebnisse für Th und U zeigen eine gute Übereinstimmung mit den nach Ende des Standardisierungsprogramms von CANMET empfohlenen Werten.Am Beispiel der Analyse von 10 geochemisch relevanten Elementen von zwei Bohrkernen einer Uranlagerstätte und Nebengesteinen wird die Anwendung der Funken-Massenspektrometrie für geologische Fragestellungen dargestellt.