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Structure and Reactivity of Sodium Phenoxide ‐ Following the Course of the Kolbe‐Schmitt Reaction
Author(s) -
Kunert Michael,
Dinjus Eckhard,
Nauck Maria,
Sieler Joachim
Publication year - 1997
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19971301017
Subject(s) - chemistry , solvent , sodium , reactivity (psychology) , crystal structure , polymer chemistry , medicinal chemistry , urea , stereochemistry , crystallography , organic chemistry , medicine , alternative medicine , pathology
Solvent‐free sodium phenoxide (NaOPh) crystallises as a polymer and forms a polymeric chain in the [0 0 1] direction. The low coordination of the sodium atoms, as evident in the crystal structure, is confirmed by the easy coordination of oxoligands (α‐donors). Hence, the four‐membered ring chain of the solvent‐free sodium phenoxide is separated by oxoligands, and forms partial structures as the polymer fragments. Thus, NaOPh crystallises in THF with the formation of an Na 6 O 6 core, consisting of two face‐fused heterocubes, and in N, N, N′, N′‐tetramethyl urea (TMU) with the formation of a Na 4 O 4 heterocubane. The solvent‐free NaOPh‐CO 2 complex obtained from the addition of CO 2 to a solution of sodium phenoxide is, when exposed to a temperature of 80°C, subject to an irreversible phase transition, as demonstrated by FT‐IR and DTA studies. The complex formed at 80°C is, apparently, another intermediate of the Kolbe‐Schmitt reaction.