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Structure and Reactivity of Sodium Phenoxide ‐ Following the Course of the Kolbe‐Schmitt Reaction

1997/10/01 by M. Kunert, Eckhard Dinjus, Maria Nauck +1 · 2 citations
Chemical Engineering · Chemistry · Materials Science · #Carbon dioxide utilization in catalysis #Metal-Organic Frameworks: Synthesis and Applications #Polyoxometalates: Synthesis and Applications

paper · doi:10.1002/cber.19971301017

openalex publication_date 1997/10/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/05/21

Abstract

Abstract 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.

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