Issue 2, 2014

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

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)

Supplementary files

Article information

Article type
Paper
Submitted
27 Aug 2013
Accepted
03 Oct 2013
First published
03 Oct 2013

Dalton Trans., 2014,43, 831-840

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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