Multiple bonding versus cage formation in organophosphorus compounds: the gas-phase structures of tricyclo-P3(CBut)2Cl and PCBut determined by electron diffraction and computational methods

Derek A. Wann, Sarah L. Masters, Heather E. Robertson, Michael Green, Richard J. Kilby, Christopher A. Russell, Cameron Jones, David W. H. Rankin

Research output: Contribution to journalArticlepeer-review

Abstract

The gas-phase structures of tricyclo-P3(CBut)2Cl and PCBut have been determined by electron diffraction and associated quantum chemical calculations. Efforts to obtain detailed solid-state data for tricyclo-P3(CBut)2Cl have been thwarted by inability to prepare suitable crystalline material. Additional calculations for another tricyclic isomer of P3(CBut)2Cl and for two phosphorus-containing cyclopentadiene derivatives with pseudo-planar five-membered rings show that the experimentally observed isomer is more stable by at least 52 kJ mol-1. Calculations for the equivalent structures with P atoms replaced by CH fragments have demonstrated that a ring structure is more favourable by over 200 kJ mol-1 compared to each of two cage structures.

Original languageEnglish
Pages (from-to)5611-5616
Number of pages6
JournalDalton Transactions
Volume40
Issue number20
DOIs
Publication statusPublished - 2011

Keywords

  • MOLECULAR-ORBITAL METHODS
  • VALENCE BASIS-SETS
  • PHOSPHORUS-COMPOUNDS
  • CRYSTALLINE PHASES
  • 2ND-ROW ELEMENTS
  • AB-INITIO
  • ENERGIES

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