Construction of triangular metallomacrocycles: [M3(1,2-bis(2,2':6',2''-terpyridin-4-yl-ethynyl)benzene)3][M = Ru(II), Fe(II), 2Ru(II)Fe(II)

Complexation of a predesigned (1,2-bis(2,2':6',2'-terpyridin-4-yl-ethynyl)benzene) ligand possessing a 60 degrees angle between two terpyridines with transition metals [Fe(II) and Ru(II)] afforded the self-assembled, triangular metallomacrocycles.     

Coordination Chemistry of Acrylamide: 1. Cobalt(II) Chloride Complexes with Acrylamide – Synthesis and Crystal Structures

The molecular structures of blue dichloro‐tetrakis(acrylamide) cobalt(II), [Co{O‐OC(NH₂)CH=CH₂}₄Cl₂] ( 1 ) and pink hexakis(acrylamide)cobalt(II) tetrachlorocobaltate(II), [Co{O‐OC‐(NH₂)CH=CH₂}₆][CoCl₄] ( 2 ), characterized by single X‐ray diffraction, IR spectroscopy and elemental analyses, are described. The coordination of Co^II in 1 involves a tetragonally distorted octahedral structure with four O‐donor atoms of acrylamide in the equatorial positions and two chloride ions in the apical positions. The second complex 2 in ionic form contains Co^II cations surrounded by an octahedral array of O‐coordinated acrylamide ligands, accompanied by a [CoCl₄]^2? anion.     

13 C 183W-Kopplungen als sonde für metall—carbin-, —carbenund—alkyl-bindungen

Carbon-13 NMR data are reported for trimethyltin derivatives containing ER_n groups where E  C, Si, Ge, Sn, N, O and S including a series of cyclic amines with ring sizes from three to seven. Coupling constant values for the homologous series of fourth group derivatives give goood correlations with the electronegativity of E. The observation of the two-bond, ¦ ²J(¹¹⁹SnE¹³C) ¦ couplings only in the derivatives containing bulky R groups is rationalized by a bimolecular exchange of ER_n groups in the concentrated solutions studied.     

The enthalpy of formation of magnesium sulfate ion pairs

The enthalpies of dilution of lithium, sodium, potassium, and magnesium chloride and sulfate solutions in the range 0.1 to 1.0 m have been measured at 30°C with a microcalorimeter. The relative apparent enthalpies φ_L of these solutions have been determined with the aid of an extended form of the Debye-Hückel limiting law $$\phi _L = S_H I^{1/2} [1/(1 + I^{1/2} ) - (\sigma /3)] + {\rm B}{\rm I} + CI^{3/2} $$ whereS _H is the limiting-law slope, σ = 3/I^3/2 × [(1+I^1/2 ? 1/(1+I^1/2 ? 2 ln (2+I^1/2)], andB andC are empirical constants. This equation fits the experimental results to within a standard deviation of 2 cal-mole^?1 for all the salts. The measured φ_L for the MgSO₄ solutions were compared to those calculated using the additivity principle, φ_L(MgCl₂) + φ_L(Na₂SO₄) ? 2φ_L(NaCl), and the extended Debye-Hückel equation. The results of this comparison have been used to calculate the ΔH _A ^o for the formation of MgSO ₄ ⁰ . A value of ΔH _A ^o = 1.15 to 1.36 was obtained, depending upon the φ_L estimates for the free ions Mg²⁺ and SO ₄ ^2? . The results are briefly discussed and compared to the results obtained by other workers.     

Measurement of PCDDs, PCDFs, and non-ortho-PCBs by comprehensive two-dimensional gas chromatography-isotope dilution time-of-flight mass spectrometry (GC x GC-IDTOFMS)

Comprehensive two-dimensional gas chromatography with isotope-dilution time-of-flight mass spectrometry (GC × GC-IDTOFMS) was used to measure polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF), and coplanar polychlorinated biphenyl (cPCB) concentrations in ash, sediment, vegetation, and fish samples. The GC × GC capability was achieved by using a quad jet, dual stage, thermal modulator. Zone compression of the GC peaks from modulation resulted in a significant increase of the signal intensity over classical GC-IDTOFMS. The GC × GC column set used an Rtx-Dioxin 2 phase as the first dimension (¹D) and an Rtx-500 as the second dimension (²D). The chromatographic separation of the 17 PCDD/Fs and the 4 cPCBs was attained in ¹D except for 2,3,7,8-TCDD and CB126 for which deconvoluted ion currents (DIC) were required to be reported separately. The Rtx-500 phase separated the bulk matrix interfering compounds from the target analytes in ²D. The instrumental limit of detection (iLODs) was 0.5 pg for 2,3,7,8-TCDD. The calibration curves showed good correlation coefficients for all the compounds investigated in the concentration range of 0.5–200 pg. GC × GC-IDTOFMS results compared favorably to those from conventional isotope-dilution one-dimensional gas chromatography-high resolution mass spectrometry (GC-IDHRMS). The comprehensive mass analysis of the TOFMS further permitted the identification of other contaminants of concern in the samples.     

Highly substituted azulene dyes as multifunctional NLO and electron-transfer compounds

Two highly substituted azulene derivatives were synthesised by Pd-mediated dimerisation from the corresponding tolan species. One azulene derivative (2) has donor functionalities (dianisylaminophenyl and dianisylamino) in the 1-, 2-, 3- and 6-positions, while the other (1) has donors (dianisylaminophenyl) in the 2- and 6-positions and acceptors (nitrophenyl) in the 1- and 3-positions. Each azulene derivative shows strong bond length alternation in the solid state, determined by X-ray crystal analysis, and an intense CT band around 450-500 nm in its UV/Vis spectrum. The first-order hyperpolarisability of 1 and of 2 was measured by hyper-Rayleigh scattering and is about that of disperse red DR1. Both azulene derivatives show multiple oxidation processes. The intramolecular adiabatic ET behaviour of the mixed valence radical cations of 1 and of 2 was investigated by UV/Vis/NIR spectroelectrochemistry. The intervalence-CT band of 1(+) could be analysed by the Generalised Mulliken-Hush theory, which yields an electronic coupling V=1140 cm(-1) for the optically induced adiabatic hole transfer.     

Partial-filling affinity capillary electrophoresis

Partial-filling affinity capillary electrophoresis (PFACE) is used to examine the binding interactions between two model biological systems: D-Ala-D-Ala terminus peptides to the glycopeptide antibiotic vancomycin (Van) from Streptomyces orientalis, and arylsulfonamides to carbonic anhydrase B (CAB, EC 4.2.1.1, bovine erythrocytes). Using these two systems, modifications in the PFACE technique are demonstrated including flow-through PFACE (FTPFACE), competitive flow-through PFACE (CFTPFACE), on-column ligand synthesis PFACE (OCLSPFACE), and multiple-step ligand injection PFACE (MSLIPFACE). In PFACE small plugs of sample are injected into the capillary column and an equilibrium is established between receptor and ligand during electrophoresis. Binding constants are then obtained by Scatchard analysis using changes in the migration time of the receptor/ligand on changing the concentration of the ligand/receptor. Data demonstrating the quantitative potential of these methods are presented. This review focuses on the unique capabilities of the different PFACE techniques as applied to two model biological systems.     

Speciation of sulfur-containing compounds in diesel by comprehensive two-dimensional gas chromatography

Sulfur-containing compounds in diesel have been speciated by comprehensive two-dimensional gas chromatography (GCxGC) with a sulfur chemiluminescence detector (SCD). The advantages of GCxGC technique are higher resolution and greater sensitivity. GCxGC-SCD can achieve the class separation of sulfur-containing compounds with an appropriate separation column combination. The major classes of sulfur-containing compounds in diesel are benzothiophenes and dibenzothiophenes. Relative concentration of each class as well as each carbon number family can be quantitated by the summation of the integrated areas corresponding to the individual group(s) in the GCxGC space. In practical applications, GCxGC-SCD can be used to characterize different diesels and to reflect desulfurization process efficiency. In this study, GCxGC-SCD has demonstrated its value in speciation of sulfur-containing compounds classes, which is difficult to accomplish by any other single technique.     

Metallorganische verbindungen der lanthanoide CVIII. Synthese und strukturaufklärung monomerer organolanthanoidacetate

LnCl₃ reacts with Na(C₅Me₄¹Bu) in THF to form the organolanthanoid chlorides [(C₅Me₄¹Bu)₂LnCl(THF)] (Ln = La (1a), Lu (1b)). Compounds 1a and 1b yield in reaction with NaO₂CCH₃ the monomeric organolanthanoid acetates [(C₅Me₄¹Bu)₂LnO₂CCH₃] (Ln = La (2a), Lu (2b)). The single crystal X-ray structure analysis of 2b as well as the cryoscopic molecular weight investigation of 2a verify the monomeric structure of these complexes.     

Ni(III) vs. Ni(II)-thiyl radical: charge-delocalisation in a binuclear Ni(III)Ni(II)-dithiolate complex

Multi-frequency EPR spectroscopy on 61Ni-labelled samples of [Ni2(L)]3+ confirms extensive charge-delocalisation between the Ni(III) centre and thiolate donors in the Ni(II)Ni(III) complex.