Primary phosphines studied by gas-phase electron diffraction and quantum chemical calculations. Are they different from amines?

Robert Noble-Eddy, Sarah L. Masters, David W. H. Rankin, Derek A. Wann, Heather E. Robertson, Brahim Khater, Jean-Claude Guillemin

Research output: Contribution to journalArticlepeer-review

Abstract

The molecular structures of allyl-, allenyl-, propargyl-, vinyl-, ethynyl-, phenyl-, benzyl-, and chloromethyl- phosphine have been determined from gas-phase electron diffraction data employing the SARACEN method. The experimental geometric parameters are compared with those obtained using ab initio calculations performed at the MP2 level using both Pople-type basis sets and the correlation-consistent basis sets of Dunning. The structure and conformational behavior of each molecule have been analyzed and, where possible, comparisons made to the analogous amine. For systems with multiple conformers, differences in the CCP bond angle of similar to 5 degrees between conformers are common. Trends in the key parameters are identified and compared with those found in similar systems.

Original languageEnglish
Pages (from-to)8603-8612
Number of pages10
JournalInorganic Chemistry
Volume48
DOIs
Publication statusPublished - 2009

Keywords

  • MOLECULAR-ORBITAL METHODS
  • GAUSSIAN-BASIS SETS
  • VALENCE BASIS-SETS
  • N-GAUCHE ROTAMER
  • MICROWAVE-SPECTRUM
  • DIPOLE-MOMENT
  • CONFORMATIONAL PROPERTIES
  • INTERNAL-ROTATION
  • WAVE-FUNCTIONS
  • AB-INITIO

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