• Please log in or register to access this feature.

Full Paper

Island Homoaromaticity in the W-Shaped 2,4-Diphospha-3-arsapentadienide Anion and Related Compounds – Theoretical and Experimental Investigations

  1. Alexander B. Rozhenko1,2,
  2. Alexander Ruban1,3,
  3. Vera Thelen3,
  4. Martin Nieger3,4,
  5. Karri Airola5,
  6. Wolfgang W. Schoeller2,6,
  7. Edgar Niecke3

Article first published online: 11 APR 2012

DOI: 10.1002/ejic.201101360

Issue

European Journal of Inorganic Chemistry

European Journal of Inorganic Chemistry

Volume 2012, Issue 15, pages 2502–2507, May 2012

Additional Information

How to Cite

Rozhenko, A. B., Ruban, A., Thelen, V., Nieger, M., Airola, K., Schoeller, W. W. and Niecke, E. (2012), Island Homoaromaticity in the W-Shaped 2,4-Diphospha-3-arsapentadienide Anion and Related Compounds – Theoretical and Experimental Investigations. Eur. J. Inorg. Chem., 2012: 2502–2507. doi: 10.1002/ejic.201101360

Author Information

  1. 1

    Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Murmans'ka str. 5, 02660 Kyiv, Ukraine, Fax: +380-44-573-2543

  2. 2

    Fakultät für Chemie der Universität Bielefeld, Postfach 100131, 33501 Bielefeld, Germany

  3. 3

    Anorganisch-Chemisches Institut der Universität Bonn, Gerhard-Domagk-Str. 1, 5300 Bonn, Germany

  4. 4

    Laboratory of Inorganic Chemistry, Department of Chemistry, University of Helsinki, P. O. Box 55 (A.I. Virtasen aukio 1), 00014 University of Helsinki, Finland

  5. 5

    Department of Chemistry, University of Jyväskylä, P. O. Box 35, 40114 Jyväskylä, Finland

  6. 6

    Department of Chemistry, University of California, Riverside, CA 92521-0403, USA

Publication History

  1. Issue published online: 14 MAY 2012
  2. Article first published online: 11 APR 2012
  3. Manuscript Received: 5 DEC 2011

SEARCH

SEARCH BY CITATION

ARTICLE TOOLS

View Full Article with Supporting Information (HTML) Get PDF (406K)

Keywords:

  • Ab initio calculations;
  • Density functional calculations;
  • Anions;
  • Homoaromaticity;
  • Molecular orbitals

Abstract

A series of anions with general formula (R2C=P)2Pn– (Pn = N, P, As, Sb; R = H, Me, CF3, SiH3, SiMe3, SiF3) was investigated theoretically at the DFT (RI-BP86/TZVP) and RI-MP2/TZVP levels of approximation. Significantly sharpened central PPnP bond angles were predicted for the species with π-acceptor R substituents. The corresponding bond angle values decrease in the order Pn = N >> P > As > Sb. This finding is in agreement with the previously published structural data for [(Me3Si)2C=P]2P–. An island homoaromaticity was proposed as a suitable explanation for the observed effect. In more detail, it consists of shifting negative charge to the electron-withdrawing terminal groups with formation of a homologue of an aromatic heterocyclopropylium cation as the central moiety. Calculated structures and charge distributions are in agreement with the proposed model as well as with the molecular structure of the newly synthesized 2,4-diphospha-3-arsapentadienyl anion.

View Full Article with Supporting Information (HTML) Get PDF (406K)