Enthalpies of formation of adducts of antimony(III) iodide with pyridine and methyl-pyridines

Abstract

Solid adducts of formula SbI 3·L (L = pyridine or 2-, 3- or 4-methylpyridine abbreviated as Py, 2MPy, 3MPy or 4MPy) were synthesized and characterized by elemental analysis, IR spectroscopy and thermal analysis. IR data showed that coordination to antimony is through nitrogen. Thermal degradation of adducts starts at 431, 423, 413 and 411 K for Py, 2MPy, 3MPy and 4MPy, respectively. Reaction-solution calorimetry was used to evaluate the enthalpy change of reaction: SbI 3(cr) + L(l) = SbI 3·L(cr), 61.13 ± 1.75, −82.60 ± 1.55, −67.50 ± 0.97 and −74.10 ± 1.19 kJ mol −1, respectively. Enthalpy change values for decomposition of adducts, lattice enthalpies and enthalpies of the Lewis acid–base reaction in the gas phase were calculated through appropriate thermochemical cycles. Mean Sb N bond enthalpies were estimated as 134 ± 3, 154 ± 3, 140 ± 3 and 147 ± 4 kJ mol −1, for Py, 2MPy, 3MPy and 4MPy, respectively.