Bonding in PF2Cl, PF3Cl, and PF4Cl: Insight into isomerism and apicophilicity from ab initio calculations and the recoupled pair bonding model

Jeff Leiding, David E. Woon, Thom H. Dunning

Research output: Contribution to journalArticle

Abstract

Following previous work on PFn and SFnCl compounds, we report high-level ab initio quantum chemical calculations on PF2Cl, PF3Cl, and PF4Cl. Coupled cluster (CCSD(T)) calculations were used to determine the structures and energetics of the various PFnCl isomers, while generalized valence bond calculations were used to gain a deeper understanding of the factors influencing the structure and energetics of the isomers. Muetterties' rule, which predicts that more electronegative elements occupy the apical positions in pentavalent phosphorus compounds, is examined in the context of the recoupled pair bonding model, which provides invaluable insights into the bonding, structure, and reactivity of hypervalent compounds. While we found more electronegative fluorine is favored in the apical position in closed-shell PF4Cl, the opposite is true for PF3Cl and two triplet excited state isomers of PF2Cl, all of which are open-shell species.

Original languageEnglish (US)
Pages (from-to)1-9
Number of pages9
JournalTheoretical Chemistry Accounts
Volume133
Issue number2
DOIs
StatePublished - Jan 1 2014

Keywords

  • Apicophilicity
  • Bent's rule
  • Hypervalency
  • Muetterties' rule
  • Pentavalent phosphorus
  • Phosphorus chlorofluorides
  • Recoupled pair bond

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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