Research papers - abstracts

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  1. G. Allen, M. Barnard, J. Emsley, N.L. Paddock and R.F.M. White, 'Trimeric and Tetrameric Phosphonitrilic Fluoride Chlorides', Chem. & Ind., 1963, 952.

    2. The isolation of all seven trimeric phosphonitrilics fluoride-chlorides, P3N3FnCl6-n, from the products of the reaction of the trimeric chloride with potassium fluoride and sulphur dioxide are reported, along with eight geminally substituted tetrameric phosphonitrilic fluoride-chlorides, P4N4FnCl8-n.

  2. J. Emsley and P.B. Udy, 'Polymerization of Hexachlorotriphosphonitrile, (NPCl2)3', Polymer, 1972, 13, 593.

    3. The discovery that the acidity of the walls of the glass reaction tube markedly affects the polymerisation of (NPCl2)3 is reported. The effects of temperature and time on the nature of the products are also discussed. An alternative cationic polymerisation mechanism is proposed.

  3. M.F. Crook, J. Emsley, T.B. Middleton and J.K. Williams, '2,2,3,4,4-Pentamethylphosphetan Acid Anhydride, C8H16P(O)OP(O)C8H16. A Compound with a Relatively Unreactive P-O-P Bond', Phosphorus and Sulfur, 1973, 3, 45.

    4. The P-O-P bond formed between two phosphetan moieties is believed to be the most stable such bond reported to date. This acid anhydride resists nucleophilic attack but can be hydrolysed by concentrated NaOH solution.

  4. J. Emsley and D.W. Griffiths, 'Trithiolan Complexes of Palladium and Platinum', J. Chem. Res., 1979, 251.

    5. The trithiolans form complexes with palladium and platinum, attaching themselves to the metal via the sulphur ring which in most cases remains intact. All the complexes are insoluble yellow solids and characterisation relies mainly on elemental analysis.

  5. J. Emsley, J. Lucas and R.E. Overill, 'Fluoride Solutions in Carboxylic Acids', Chem. Phys. Letts., 1981, 84, 593; ibid, 1982, 88, 522.

    6. Solutions of KF in glacial acetic acid involve three hydrogen-bonded species in equilibrium:
    2CH3CO2HF- = HF2- + H(CH3CO2)2- (1)
    Ab initio calculations, on the formic acid system, show that the isolated ion HCO2HF- is the most stable species. However, with a solvent sphere model the right hand side of equation (1) is favoured.

  6. J. Emsley, J. Lucas and R.E. Overill, 'Potassium Fluoride and Phosphorous Acid: Ab initio Calculations and Spectroscopic Investigations', Polyhedron, 1983, 2, 19.

    7. Ab initio calculations including the effects of salvation on the hydrogen bonding interactions between F- and phosphorous acid, HPO3H2, have been performed, resulting in a value of 61 kJ mol-1 for the hydrogen bond energy of [HPO3H2F]-. Attempts to show that this species exists in aqueous solution have been made using 17O, 19F and 31P NMP spectroscopy and pH and conductance studies, but these indicate that the principal reaction is an acid-base neutralisation. Crystals of KF.HPO3H2 grow from aqueous solution but these are not the same as those from methanol solution which are known to be strongly hydrogen bonded.

  7. J. Emsley and S.B. Niazi, 'The Chemical Phosphorylation of myo-Inositol', Soil Biol. Biochem., 1984, 16, 73.

    8. Attempts of phosphorylate myo-inositol with various polyphosphates our urea-phosphate under aqueous conditions proved unsuccessful, despite reports to the contrary. The easiest way to phosphorylate myo-inositol is to heat it with H3PO4 under reduced pressure at 150°C for 6h.

  8. J. Emsley and S.B. Niazi, 'Hydrolysis of Na5P3O10 at 100°C: Effect of NaF', Phys. Chem., 1986, 5, 93.

    9. First order rate constant for the hydrolysis of Na5P3O10 in the presence of 1:1 mole NaF are reported as 2.05 x 10-1, 9.67 x 10-2 and 4.95 x 10-2 hr-1 at pHs 7.0, 8.0 and 10.0 respectively. With 1:3 mole NaF the rate constant is 2.25 x 10-1 hr-1. The presence of fluoride ion has a retarding effect. These observations are explained by hydrogen bonding of the fluoride. The course of reaction is followed by 31P NMR spectroscopy.