Effects of ligand electronegativity on recoupled pair bonds with application to sulfurane precursors

Beth A. Lindquist, David E Woon, Thom H. Dunning

Research output: Contribution to journalArticle

Abstract

Recoupled pair bonds (RPBs) are conditional bonds-they only form for selected central atoms and ligands. A complete theoretical description of RPBs requires an understanding of the properties of the central atom and ligands that enable such bonds to be formed. In this work, we show that ligand electronegativity is positively correlated with recoupled pair bond strength for a variety of ligands interacting with the 3p2 pair of sulfur. We also describe substituent (X) effects on the SF(a4-) state by investigating X2SF species. These effects generally mirror those observed for covalently bound analogues, but we found that recoupled pair bonding can lead to breakdowns in the expected relationships among bond length, strength, and force constant for some of these species. Finally, we compare the properties of two molecules of practical interest that are bound by recoupled pair bonds: the dimethyl sulfur fluoride and hydroxide radicals (DMS-F and DMS-OH).

Original languageEnglish (US)
Pages (from-to)5709-5719
Number of pages11
JournalJournal of Physical Chemistry A
Volume118
Issue number30
DOIs
StatePublished - Jul 31 2014

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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