The thermal decomposition of alkaline earth formates

The thermal decomposition of alkaline earth formates has been studied. Experiments with single crystals, compacts and powders of strontium formate demonstrate that the method of sample presentation can affect the rate of decomposition.For anhydrous calcuim, strontium and barium formates, isothermal kinetic runs show that the decompositions follow the Erofeev law, In(l-α) = ktⁿ; the measured activation energies were 199.4, 228 and 270 kJ/mol respectively.     

Regioselective hydroborations of methylvinylchlorosilanes

The regioselectivity of the hydroboration of the methylchlorovinylsilanes, Cl_nMe_3?nSiCHCH₂ (n= 0 ? 3), has been investigated using BH₃←THF, 9-BBN, disiamyl- and dicyclohexylborane. Methylation of the adducts with methylmagnesium bromide is complicated by formation of tetraalkylboronates. Alkaline hydrogen peroxide oxidation of the boronates gives reasonable yields of the corresponding α- and β-trimethylsilylethanols forn= 0 and 1. Forn= 2 and 3, conversion of the adducts to the corresponding α- and β- deuteroethylsilanes by treatment with excess sodium methoxide in methanol-0-d provides a more effective means of derivatization. Addition of the alkenes,n= 2 or 3, to excess BH₃←THF givesca. 90% of the α-boro-organo-chlorosilanes. For all of the alkenes, the dialkylboranes giveca. 80% of the β-boron adducts.     

Thermodynamics for Coulomb systems: A problem at vanishing particle densities

In this paper I combine techniques recently developed by Charles Fefferman with the well-known methods of Joel Lebowitz and Elliott Lieb to resolve some technical problems left unsettled by Lebowitz and Lieb's fundamental 1972 paper The constitution of matter: Existence of thermodynamics for systems composed of electrons and nuclei.     

Versatile organic (fullerene)-inorganic (CdTe nanoparticle) nanoensembles

Novel organic (positively charged fullerene)-inorganic (negatively charged CdTe nanoparticle) nanoensembles were devised through electrostatic interactions and probed as versatile donor-acceptor hybrids. Photoirradiation of their homogeneous solutions, containing the electrostatically packed components, let to very long-lived (1.3 ms) charge separated states.     

The chemistry of phosphole derivatives

Synthetic approaches to, and the chemistry of, phospholes, benzophospholes and dibenzophospholes are reviewed and particular attention is paid to the possible aromatic character of the phosphole ring. Systems containing the 2H- and 3H-phosph(V)ole nucleus are surveyed as are phosphole derivatives containing pentacovalent and six-coordinate phosphorus. Stereochemical considerations in the more complex phosphole derivatives are discussed.     

A quantum-mechanical study of the lone-pairs in H2O and H2S

It is shown from SCF-MO studies using localised orbitals that the angles between the lone-pairs in H₂O and H₂S are 115° and 127°, in agreement with the qualitative predictions of the Sidgwick-Powell theory.     

Reactions of C(6)F(5)Li with tetracyclone and 3-ferrocenyl-2,4, 5-triphenylcyclopentadienone: An (19)F NMR and X-ray crystallographic study of hindered pentafluorophenyl rotations

Tetracyclone, 2a, reacts with C(6)F(5)Li to yield 2-pentafluorophenyl-2,3,4,5-tetraphenylcyclopent-3-en-1-one, 7, and 5-hydroxy-5-pentafluorophenyl-1,2,3,4-tetraphenylcyclopentadiene, 8, as the result of 1,6 and 1,2 additions, respectively. In contrast, treatment of 3-ferrocenyl-2,4,5-triphenylcyclopentadienone, 2b, with lithiopentafluorobenzene leads to 4-ferrocenyl-4-pentafluorophenyl-2, 3,5-triphenylcyclopent-2-en-1-one, 9, and 5-hydroxy-5-pentafluorophenyl-2-ferrocenyl-1,3, 4-triphenylcyclopentadiene, 10, the products of 1,4 and 1,2 addition, respectively. The structures of 7-9 have been established by X-ray crystallography, and the barriers to rotation (19-21 kcal mol(-)(1)) of the pentafluorophenyl groups in 8-10 have been studied by variable-temperature (19)F NMR. Nucleophilic attack at the ferrocenyl-bearing carbon in 2b is rationalized in terms of a zwitterionic structure in which the positive charge of the "cyclopentadienyl cation" is delocalized onto the iron atom in the organometallic substituent.     

Separation scheme for the determination of alkali metals (K, Rb, Cs), alkaline earths (Sr, Ba) and rare earths (Ce, Nd, Sm, Eu) in silicate materials by isotopic dilution analysis

A scheme is outlined for the separation of Li, K, Rb, Cs, Sr, Ba, Ce, Nd, Sm and Eu from silicate materials. The elements are separated by cation-exchange to provide groups suitable for mass spectrometric analysis, and are then further purified by anion-exchange. Results obtained by isotopic dilution analysis are reported for G-1, W-1, and the Harwell meteorite-in these measurements the alkali metals were determined separately from the other elements. Requirements are discussed for combining the procedures to form a more comprehensive method for use with a single sample.     

Observation of apigenin anionic clusters in the gas phase

The ubiquity and favorable medicinal properties of flavonoids make essential the determination of flavonoid levels in various matrices. While developing a liquid chromatography/tandem mass spectrometry method for the analysis of the flavonoid, apigenin, anionic oligomers and nitrate- and chloride-bound clusters of this compound were observed. Tandem mass spectrometry of these oligomers and cluster ions showed the cleavage of apigenin molecules from the precursor. The observation of these cluster ions shows the possibility of post-column derivatization techniques to enhance specificity in analysis. Copyright 2000 John Wiley & Sons, Ltd.