Metaphosphate and Tris(methylene)metaphosphate (P(CH2)3 -) Anions. Do They Have Three Double Bonds to Phosphorus?

Andrzej Rajca, Julia E. Rice, Andrew Streitwieser, Henry F. Schaefer

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Abstract

Ab initio studies are presented for metaphosphate ion, P03- (1), and tris(methylene)metaphosphate ion, P(CH2)3- (2). Using good basis sets at the SCF level, the minimum energy structure of 2 is a D3structure with the CH2groups twisted by 19° from the molecular plane, but this structure lies only 1 kcal mol-1below the constrained D3hplanar structure. Inclusion of electron correlation increases this energy difference by only 1 kcal mol-1. The charge distributions correspond to highly polar structures with large negative charges on the oxygens and methylene groups of P03- and P(CH2)3-, respectively. The best simple representation of these compounds is as dipolar structures; double bonding to phosphorus is relatively weak.

Original languageEnglish (US)
Pages (from-to)4189-4192
Number of pages4
JournalJournal of the American Chemical Society
Volume109
Issue number14
DOIs
StatePublished - Jul 1 1987

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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