On the Nature of the 7-Norbornadienyllithiums. Preliminary Communication

Lithium reductions of 7-chloronorbornadiene and of bis(7-norbornadienyl)mercury both provide (C₇H₇)₂Li₂ ( 5a ). This product is accompanied by C₇H₇Li₂Cl ( 5c ) in the first case, and by C₇H₇Li ( 5b ) in the second. The theoretically anticipated properties of all three organolithiums are apparent in the consistent C_s symmetry of their hydrocarbon ligands, their protolytic destruction by 12-crown-4, and their significant J(C(7), Li) ( 5a , 7.6; 5b , 16.0; 5c 8.9 Hz).     

One-step cleanup for PAH residue analysis in plant matrices using size-exclusion chromatography

A new one-step cleanup procedure, based on size-exclusion chromatography (SEC), usable for the extracts from accelerated solvent extraction (ASE), Soxhlet extraction, or ultrasonic extraction (USE), is described. The method is suitable for the determination of polycyclic aromatic hydrocarbons (PAHs), especially from very complicated plant matrices (e.g. pine needles, deciduous leaves, mosses). The main improvement compared with previous conventional procedures is that analyte peaks barely overlap with matrix peaks in the chromatograms and that it is a very rapid and simple one-step procedure with clearly improved analytical performance. Essential advantages of this SEC procedure are the sharper GC-MS chromatograms for the PAH fraction at retention times between 9.2 and 12.0 min, distinctly separated substance peaks resulting in better analysis, shorter running times, and lower solvent consumption.     

The electric field gradient at111Cd in vanadium oxides

The electric field gradient (efg) of¹¹¹Cd in polycrystalline V₂O₅ was studied using perturbed angular correlation (PAC) spectroscopy, with the¹¹¹In activity ion-implanted at 400 keV. Between the individual steps of an isochronal annealing program, a distinct efg (v _Q 1=88.1(3) MHz, ₁=0.62(2)) was recorded the contribution of which increased with annealing temperature up to 74% at 870 K. Corresponding X-ray analysis of inactive V₂O₅ samples, which underwent the same annealing treatment, proved that the sample always stayed as V₂O₅. Since V₂O₅ has only one equivalent cation site, it is concluded that this efg belongs to¹¹¹Cd at this site. Oxidation of a vanadium foil atT=675 and 800 K at =200 mbar also yielded this efg. From PAC measurements in VO₂, two well-defined efg's were found above and below the metal-semiconductor transition at 340 K, which are tentatively attributed to the monoclinic and the tetragonal phase.Supported by Deutsche Forschungsgemeinschaft and DAAD.On leave from the University of Durban-Westville, South Africa.     

Configuration interaction (CI): Approximate inclusion of fourfold and threefold excitations,an application of knowledge engineering

It is shown that even the CPMET approximation for the contributions of fourfold excitations can be replaced by a more sophisticated method. Furthermore, an approximation is presented for the contributions of threefold excitations which are neglected in CPMET . Finally, it is described how the advantages of different CEPA methods can be united in a single CEPA scheme (called CEPA -U). The various approximations are discussed in terms of Slater determinants, and it is shown how the relatively large amount of details can be handled with the help of computer programs, i.e., how knowledge engineering can be successfully applied here.     

Spectrophotometric determination of phosphate by extraction of reduced molybdoantimonylphosphoric acid with acetophenone-chloroform

A 90% ($\text{v}\text{v}$) mixture of acetophenone-chloroform is an effective extractant for reduced molybdoantimonylphosphoric acid. The extraction is quantitative over the acidity range of 0.04 to 4.8 N sulfuric acid. The mixed solvent extractant is virtually immiscible with water and can be used at aqueous/organic volume ratios from 1:1 to 40:1 with no loss of solvent or decrease in % extraction. Phosphate is easily determined from 5 to 1000 ppb. No interference from silicate was experienced.     

Supramolecular phthalocyanine dimers based on the secondary dialkylammonium cation/dibenzo-24-crown-8 recognition motif

[formula: see text] New unsymmetrically substituted DB24C8-phthalocyanines, which are able to form complexes with suitable dialkylammonium cations, have been prepared. These complexes most probably have a pseudorotaxane geometry.