P. N. Gates

Phosphorus halide–boron halide complexes. Part I. The infrared spectrum of PI3,BI3

The infrared spectrum of the complex Pl2,Bl3 has been measured in the solid state between 30 and 1000 cm.–1. Normal co-ordinate calculations show that the best fit to experimental data is obtained by assuming a force constant for the stretching of the P–B bond of 1·0 millidyne per A. The P–B bond dissociation energy has been estimated to be ca. 16 kcal. mole–1.

Mixed halogen complexes of phosphorus. Part I. Preparation and Raman spectra of the chlorobromophosphonium ions, [PClnBr4–n]+(0 ⩽n⩽ 4)

The preparation of some complexes and mixtures containing the PCl3Br+, PCl2Br2+ and PClBr3+ ions is described. A vibrational assignment for each species has been made based on data from Raman spectra of the complexes in the solid state. Some characteristic shifts occur in the fundamental frequencies of the phosphonium ions where single halide or polyhalide anions are present in the crystal lattice. It is suggested that such vibrational frequencies can be used to infer (a) the structures of complexes involving phosphonium ions and (b) the presence or absence of single halide or trihalide ions in the lattice.

Standard enthalpy of formation of dichloroiodine(III) tetrachloroaluminium(III), [ICl2+] [AlCl4−] and the thermochemistry and energetics of the gaseous dichloroiodine(III) cation, [ICl2+]

Abstract The experimental determination of the standard enthalpy of formation of the crystalline salt, [ICl 2 + ][AlCl 4 − ], is reported to be Δ f H 0 (IAlCl 6 c)/kJ mol −1 = −836.6±6.2 along with the total lattice potential energy, U POT (IAlCl 6 )/kJ mol − , calculated to be 562.5±5.0 using the program LATEN. The standard enthalpy of formation of the [ICl 2 + ] cation, Δ φ H 0 ([ICl 2 + ],g)/kJ mol −1 is found to be 926.9±9.0. The electron attachment enthalpies for the ICl 2 . (g) and [ICl 2 + ] (g) species, are in kJ mol −1 , : 533.2 and −999, respectively.

Vibrational spectra and thermodynamic properties of difluoroiodophosphine

Raman and infrared spectra in the range 20–1200 cm–1 have been measured for PF2I. Vibrational assignments are made on the basis of these spectra and of approximate normal co-ordinate calculations; statistical thermodynamic functions have been calculated. Statistical thermodynamic functions for PF3 have been calculated using revised data.

The existence and vibrational characterisation of the trichlorobromophosphonium ion

The existence of the trichlorobromophosphonium ion [PCl3Br]+ has been confirmed in the solid complexes PBCl7Br and P2F6Cl3Br and a vibrational assignment is given.