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Issue 2, 2014
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Coulomb repulsion versus cycloaddition: formation of anionic four-membered rings from sodium phosphaethynolate, Na(OCP)

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Abstract

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.

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

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Publication details

The article was received on 27 Aug 2013, accepted on 03 Oct 2013 and first published on 03 Oct 2013


Article type: Paper
DOI: 10.1039/C3DT52359D
Citation: Dalton Trans., 2014,43, 831-840
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    Coulomb repulsion versus cycloaddition: formation of anionic four-membered rings from sodium phosphaethynolate, Na(OCP)

    D. Heift, Z. Benkő and H. Grützmacher, Dalton Trans., 2014, 43, 831
    DOI: 10.1039/C3DT52359D

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