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Attachment of molecular hydrogen to an isolated boron cation: an infrared and ab initio study
Faculty of Science - Papers (Archive)
  • Viktoras Dryza, University Of Melbourne
  • Berwyck L. J Poad, University of Wollongong
  • Evan J Bieske, University Of Melbourne
RIS ID
72174
Publication Date
1-1-2008
Publication Details

Dryza, V., Poad, B. L. J. & Bieske, E. J. (2008). Attachment of molecular hydrogen to an isolated boron cation: An infrared and ab initio study. Journal of the American Chemical Society, 130 (39), 12986-12991.

Abstract

Structural properties of the B+−H2 electrostatic complex are investigated through its rotationally resolved infrared spectrum in the H−H stretch region (3905−3975 cm−1). The spectrum, which was obtained by monitoring B+ photofragments while the IR wavelength was scanned, is consistent with the complex having a T-shaped structure and a vibrationally averaged intermolecular separation of 2.26 Å, which decreases by 0.04 Å when the H2 subunit is vibrationally excited. The H−H stretch transition of B+−H2 is red-shifted by 220.6 ± 1.5 cm−1 from that of the free H2 molecule, much more than for other dihydrogen complexes with comparable binding energies. Properties of B+−H2 and the related Li+−H2, Na+−H2, and Al+−H2 complexes are explored through ab initio calculations at the MP2/aug-cc-pVTZ level. The unusually large red-shift for B+−H2 is explained as due to electron donation from the H2 σg bonding orbital to the unoccupied 2pz orbital on the B+ ion.

Citation Information
Viktoras Dryza, Berwyck L. J Poad and Evan J Bieske. "Attachment of molecular hydrogen to an isolated boron cation: an infrared and ab initio study" (2008) p. 12986 - 12991
Available at: http://works.bepress.com/berwyck_poad/14/