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

Heift, D.; Benkő, Z.; Grützmacher, H.

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.

Citation

Heift, D., Benkő, Z., & Grützmacher, H. (2014). Coulomb repulsion versus cycloaddition: formation of anionic four-membered rings from sodium phosphaethynolate, Na(OCP). Dalton Transactions, 43(2), 831-840. https://doi.org/10.1039/c3dt52359d

• Journal Article Type: Article
• Acceptance Date: Oct 3, 2013
• Online Publication Date: Oct 3, 2013
• Publication Date: 2014-01
• Deposit Date: Feb 21, 2017
• Journal: Dalton Transactions
• Print ISSN: 1477-9226
• Electronic ISSN: 1477-9234
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 43
• Issue: 2
• Pages: 831-840
• DOI: https://doi.org/10.1039/c3dt52359d
• Public URL: https://durham-repository.worktribe.com/output/1363204