Thermochemistry of Li, Na, K, Rb and Cs alkylated phenoxides

Lattice energies and thermochemical radii of the anions OR− (R = 2-Me; 2,6-Me2; 2,4,6-Me3; 2,6-t-Bu2) in alkali metal phenoxides, MOR (M = Li, Na, K, Rb and Cs) were investigated based on the corresponding standard molar enthalpies of formation determined by reaction-solution calorimetry. The results obtained at 298.15 K were as follows: ΔfHm∘ (MOR, cr)/kJ mol−1 = −398.4 ± 1.1 (LiO-2-MePh), −423.4 ± 1.6 (LiO-2,6-Me2Ph), −457.3 ± 7.1 (LiO-2,4,6-Me3Ph), −346.6 ± 1.4 (NaO-2-MePh), −399.1 ± 1.5 (NaO-2,6-Me2Ph), −422.4 ± 7.1 (NaO-2,4,6-Me3Ph), −496.6 ± 7.1(NaO-2,6-t-Bu2Ph), −367.8 ± 1.2 (KO-2-MePh), −399.1 ± 1.4 (KO-2,6-Me2Ph), −368.8 ± 1.2 (RbO-2-MePh), −403.6 ± 1.3 (RbO-2,6-Me2Ph), −387.0 ± 1.6 (CsO-2-MePh) and −413.6 ± 1.3 (CsO-2,6-Me2Ph). Estimates of thermochemical raddi, lattice energies and standard enthalpies of formation of not experimentally measured alkali metal phenoxides was successfully done with a model based on the Kapustinskii equation and the set of values experimentally determined.