On the Molecular and Electronic Structures of AsP3 and P 4

Brandi M. Cossairt, Christopher C. Cummins, Ashley R. Head, Dennis L. Lichtenberger, Raphael J.F. Berger, Stuart A. Hayes, Norbert W. Mitzel, Gang Wu

Research output: Contribution to journalArticle

49 Scopus citations

Abstract

The molecular and electronic structures of AsP3 and P 4 have been investigated. Gas-phase electron diffraction studies of AsP3 have provided rg bond lengths of 2.3041(12) and 2.1949(28) Å for the As-P interatomic distances and the P-P interatomic distances, respectively. The gas-phase electron diffraction structure of P 4 has been redetermined and provides an updated value of 2.1994(3) Å for the P-P interatomic distances, reconciling conflicting literature values. Gas-phase photoelectron spectroscopy provides experimental values for the energies of ionizations from the valence molecular orbitals of AsP 3 and P4 and shows that electronically AsP3 and P4 are quite similar. Solid-state 75As and 31P NMR spectroscopy demonstrate the plastic nature of AsP3 and P 4 as solids, and an extreme upfield 75As chemical shift has been confirmed for the As atom in AsP3. Finally, quantum chemical gauge-including magnetically induced current calculations show that AsP 3 and P4 can accurately be described as strongly aromatic. Together these data provide a cohesive description of the molecular and electronic properties of these two tetraatomic molecules.

Original languageEnglish (US)
Pages (from-to)8459-8465
Number of pages7
JournalJournal of the American Chemical Society
Volume132
Issue number24
DOIs
StatePublished - Jun 23 2010

ASJC Scopus subject areas

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

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    Cossairt, B. M., Cummins, C. C., Head, A. R., Lichtenberger, D. L., Berger, R. J. F., Hayes, S. A., Mitzel, N. W., & Wu, G. (2010). On the Molecular and Electronic Structures of AsP3 and P 4. Journal of the American Chemical Society, 132(24), 8459-8465. https://doi.org/10.1021/ja102580d