Intramolecular carboxylic acid trapping of pyran-4-one derived zwitterions: A novel synthesis of fused bicyclic lactones

Pyran-4-ones bearing carboxylic acid side chains were prepared either by direct carboxylation with carbon dioxide or through oxidative cleavage of side chain olefins. Irradiation in a non-nucleophilic solvent yielded fused bicyclic lactones. The efficiency of the reaction was not dependent on ring substitution.     

Pentacoordinate spirosilicate anion, bis(2,2′-biphenyldiyl)methylsilicate, synthesized by the lithium cleavage of dimethoxyethane

The reaction of spirobisilafluorene (1) with lithium in dimethoxyethane produces lithium 1-methyl-spirobisilafluorenide (2), a stable pentacoordinate silicon compound with five carbon ligands, and lithium 2-methoxyethoxide, which was identified by trapping with Ph₃SiCl to give Ph₃Si-OCH2CH2OCH3 (4). The X-ray crystal structure of 2 shows that the geometry at silicon is an idealized trigonal bipyramid, slightly distorted toward a square pyramid. Methanolysis of 2 cleaves a Si-aryl bond producing a methyl biphenylsilafluorene, 3. Crystal structures are reported for 3 and 4.     

Determination of cadmium by atomic-fluorescence and atomic-absorption spectrophotometry

The adaptation of a conventional atomic-absorption/flameemission spectrophotometer to the measurement of atomic-fluorescence in an air-acetylene flame is described. The determination of cadmium on the same instrument by both atomic-fluorescence and absorption shows that, even with a rather simple and inefficient means of exciting and measuring fluorescence, results can be obtained which indicate that the fluorescence technique is considerably more sensitive than atomic-absorbance and is equally free from inter-element interference.     

N-substituted salicylaldimine complexes of rhodium(III) and related rhodium(III) organometallic derivatives

A series of new Rh^III complexes with N-substituted salicylaldimines have been prepared of the form [RhSBPy₂]PF₆ where SB is a tetradentate N,N′-substituted bis(salicylaldimine) or represents two molecules of a corresponding bidentate derivative. Several of these complexes have been reduced with 0.5% sodium amalgam and the products reacted with CH₃I to yield the organometallic derivatives CH₃RhSBPy.     

Determination of trace concentrations of citrate in aqueous systems

A fluorimetric method for the determination of citrate is described. Through a series of reactions, citrate is converted into citrazinic acid. The ammonium salt of this compound exhibits a fluorescence maximum at 430 nm when an excitation source of 340 nm is used. The method does not suffer from the normal interferences. The limit of detection is 0.01 μg ml^-, and the best working range is 0.1–10 μg ml^-1.     

Spectroscopy in separated flames-II The use of the separated air-acetylene flame in long path atomic absorption spectroscopy

The application of a separated air-acetylene flame to the determination of several elements by long-path atomic-absorption spectroscopy is described. The factors which govern the stability and reproducibility of the separated flame have been investigated. High sensitivity and stability and low background absorption are obtained in the the determination of zinc, iron, copper, mercury, magnesium and silver by the method described.     

Metal ion complexes of 2-picolinamineN-oxide

Summary A series of cobalt(II), nickel(II) and copper(II) complexes of 2-picolinamineN-oxide, HA, has been prepared. Solids of formula [M(HA)₃](BF₄)₂ (M=cobalt(II) or nickel(II); [Cu(HA)₂]X₂ (X=BF ₄ ^– , NO ₃ ^– ); [Co(HA)₂X₂] (X=Cl^– or Br^–); [Ni(HA)₂Cl₂] and [Cu(HA)X₂] (X=Cl^– or Br^–] have been isolated and characterized by partial elemental analyses, molar conductivities, magnetic susceptibilities, DSC-TGA, and spectral methods. All complexes were found to be monomeric, and their spectral parameters are compared with those of the metal ion complexes ofN-alkyl-2-picolinamineN-oxides, 2-dialkylaminopyridineN-oxides and 2-picolinamine. The cobalt(II) and nickel(II) halide complexes spectrally show a mixture of octahedral and tetrahedral centres.     

Synthesis and spectroscopic studies of metal(II) complexes prepared withN-2-(5-picolyl)-N′-phenylthiourea

Summary The chlorides and bromides of cobalt(II), nickel(II) and copper(II) along with the acetates of the latter two metal ions and copper(II) tetrafluoroborate were used to prepare complexes ofN-2-(5-picolyl)-N-phenylthiourea (5MTUH). 5MTUH coordinates as a bidentate ligand via the pyridyl nitrogen and the sulphur atoms in the cobalt(II) complexes and the compounds isolated with Cu(BF₄)₂ and CuCl₂. Complexes of stoichiometry [Cu(5MTU)X] (X=Br or C₂H₃O₂) appear to have the deprotonated ligand coordinated via the pyridyl andN thioamide nitrogens and the sulphur atom. The nickel(II) complexes involve monodentate 5MTUH with sulphur being the donor atom. A violet, octahedral [Co(5MTUH)₂Cl₂] complex and a blue, tetrahedral [Co(5MTUH)Cl₂] complex have been isolated, but with CoBr₂ only an octahedral complex could be prepared.     

A simple atmospheric microwave-excited emissive detector for gas chromatography

An atmospheric pressure microwave-excited emissive argon plasma is evaluated for use as a detector in conventional gas-chromatographic analysis. A range of carbon-, oxygen-, nitrogen- and halogen-containing compounds was investigated in order to optimize the sensitivity, linear working range and plasma operating conditions. For the non-selective determination of carbon-containing compounds, the atomic carbon emission at 247.9 nm was found to be most useful. At this wavelength the sensitivities for all the compounds investigated were directly proportional to the amount of carbon in the compounds. The limit of detection for these compounds at 247.9 nm was 1.94·10^-l0 g of carbon per sec. The atomic lines at 206.2 nm (I) and 470.5 nm (Br) were the best for the selective determination of iodine- and bromine-containing compounds respectively, and a new band emission at 256 nm, characteristic of chlorinecontaining compounds, gave good sensitivity.