On the molecular and electronic structures of AsP3 and P4

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

doi:10.1021/ja102580d

On the molecular and electronic structures of AsP3 and P4

J Am Chem Soc. 2010 Jun 23;132(24):8459-65. doi: 10.1021/ja102580d.

Authors

Brandi M Cossairt¹, Christopher C Cummins, Ashley R Head, Dennis L Lichtenberger, Raphael J F Berger, Stuart A Hayes, Norbert W Mitzel, Gang Wu

Affiliation

¹ Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA-02139, USA.

PMID: 20515032
DOI: 10.1021/ja102580d

Abstract

The molecular and electronic structures of AsP(3) and P(4) have been investigated. Gas-phase electron diffraction studies of AsP(3) have provided r(g) bond lengths of 2.3041(12) and 2.1949(28) A 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) A 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 P(4) and shows that electronically AsP(3) and P(4) are quite similar. Solid-state (75)As and (31)P NMR spectroscopy demonstrate the plastic nature of AsP(3) and P(4) as solids, and an extreme upfield (75)As chemical shift has been confirmed for the As atom in AsP(3). Finally, quantum chemical gauge-including magnetically induced current calculations show that AsP(3) and P(4) 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.