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Bonding Energetics in Alkaline Metal Alkoxides and Phenoxides
Author(s) -
Nunes Paulo,
Leal Joāo P.,
Cachata Vera,
Raminhos Henrique,
Minas da Piedade Manuel E.
Publication year - 2003
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200204447
Subject(s) - energetics , calorimetry , lattice energy , chemistry , metal , crystal structure , standard enthalpy of formation , crystallography , stereochemistry , thermodynamics , physics , organic chemistry
The bonding energetics in a variety of alkaline metal, alkoxides and phenoxides, MOR, was investigated based on the corresponding enthalpies of formation in the crystalline state determined by reaction‐solution calorimetry. The results obtained at 298.15 K were as follows: Δ f H $\rm{_{m}^{\,o}}$ (MOR, cr)/kJ mol −1 = 382.7±1.4 (LiOC 6 H 5 ), 513.6±2.5 (NaO‐ n C 6 H 13 ), 326.4±1.4 (NaOC 6 H 5 ), 375.2±3.4 (KOCH 3 ), 434.5±2.7 (KOC 2 H 5 ), 467.1±5.2 (KO‐ n C 3 H 7 ), 459.3±2.1 (KO‐ n C 4 H 9 ), 464.6±5.7 (KO‐ t C 4 H 9 ), 464.3±2.5 (KO‐ n C 6 H 13 ), 333.3±3.1 (KOC 6 H 5 ), 380.6±2.9 (RbOCH 3 ), 434.1±2.9 (RbOC 2 H 5 ), 345.3±2.9 (LiOC 6 H 5 ), 379.1±3.0 (CsOCH 3 ), 432.3±3.1 (CsOC 2 H 5 ), 466.9±5.0 (CsO‐ n C 3 H 7 ), 461.3±3.5 (CsO‐ n C 4 H 9 ), 461.9±2.5 (CsO‐ t C 4 H 9 ), 349.2±1.4 (CsOC 6 H 5 ). These results together with revised Δ f H $\rm{_{m}^{\,o}}$ (MOR, cr) values from the literature, were used to derive a consistent set of lattice energies for the MOR compounds and discuss general trends in the structure–energetics relationship based on the Kapustinskii equation.