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Coulomb repulsion versus cycloaddition: formation of anionic four-membered rings from sodium phosphaethynolate, Na(OCP)

Carbon dioxide and two equivalents of Na(OCP) form, in an equilibrium reaction, a CO2 adduct of the composition Na2(P2C3O4). The anion of this salt, [O2C-P(CO)2P](2-), is built up by a four-membered 1,3-diphosphetane-2,4-dione ring and a carboxylate unit attached to one of the phosphorus atoms. A re...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2014-01, Vol.43 (2), p.831-840
Main Authors: Heift, Dominikus, Benkő, Zoltán, Grützmacher, Hansjörg
Format: Article
Language:English
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Summary:Carbon dioxide and two equivalents of Na(OCP) form, in an equilibrium reaction, a CO2 adduct of the composition Na2(P2C3O4). The anion of this salt, [O2C-P(CO)2P](2-), is built up by a four-membered 1,3-diphosphetane-2,4-dione ring and a carboxylate unit attached to one of the phosphorus atoms. A remarkable π-delocalization was observed within the OCPCO moiety. The stepwise reaction mechanism leading to Na2(P2C3O4) was investigated with quantum chemical calculations. Accompanied by the release of CO2, Na2(P2C3O4) reacts with both 2-iodopropane and 4,4',4''-trimethoxytriphenylmethyl chloride to form four-membered cyclic anions. For comparison the analogous reactions were performed with Na(OCP) instead of Na2(P2C3O4) and the results are discussed in detail.
ISSN:1477-9226
1477-9234
DOI:10.1039/c3dt52359d