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

Rozhenko AB, Ruban A, Thelen V, Nieger M, Airola K, Schoeller W, Niecke E (2012)
European Journal of Inorganic Chemistry 2012(15): 2502-2507.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
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Abstract / Bemerkung
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 p-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.
Erscheinungsjahr
Zeitschriftentitel
European Journal of Inorganic Chemistry
Band
2012
Zeitschriftennummer
15
Seite
2502-2507
ISSN
PUB-ID

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Rozhenko AB, Ruban A, Thelen V, et al. Island Homoaromaticity in the W-Shaped 2,4-Diphospha-3-arsapentadienide Anion and Related Compounds - Theoretical and Experimental Investigations. European Journal of Inorganic Chemistry. 2012;2012(15):2502-2507.
Rozhenko, A. B., Ruban, A., Thelen, V., Nieger, M., Airola, K., Schoeller, W., & Niecke, E. (2012). Island Homoaromaticity in the W-Shaped 2,4-Diphospha-3-arsapentadienide Anion and Related Compounds - Theoretical and Experimental Investigations. European Journal of Inorganic Chemistry, 2012(15), 2502-2507. doi:10.1002/ejic.201101360
Rozhenko, A. B., Ruban, A., Thelen, V., Nieger, M., Airola, K., Schoeller, W., and Niecke, E. (2012). Island Homoaromaticity in the W-Shaped 2,4-Diphospha-3-arsapentadienide Anion and Related Compounds - Theoretical and Experimental Investigations. European Journal of Inorganic Chemistry 2012, 2502-2507.
Rozhenko, A.B., et al., 2012. Island Homoaromaticity in the W-Shaped 2,4-Diphospha-3-arsapentadienide Anion and Related Compounds - Theoretical and Experimental Investigations. European Journal of Inorganic Chemistry, 2012(15), p 2502-2507.
A.B. Rozhenko, et al., “Island Homoaromaticity in the W-Shaped 2,4-Diphospha-3-arsapentadienide Anion and Related Compounds - Theoretical and Experimental Investigations”, European Journal of Inorganic Chemistry, vol. 2012, 2012, pp. 2502-2507.
Rozhenko, A.B., Ruban, A., Thelen, V., Nieger, M., Airola, K., Schoeller, W., Niecke, E.: Island Homoaromaticity in the W-Shaped 2,4-Diphospha-3-arsapentadienide Anion and Related Compounds - Theoretical and Experimental Investigations. European Journal of Inorganic Chemistry. 2012, 2502-2507 (2012).
Rozhenko, Alexander B., Ruban, Alexander, Thelen, Vera, Nieger, Martin, Airola, Karri, Schoeller, Wolfgang, and Niecke, Edgar. “Island Homoaromaticity in the W-Shaped 2,4-Diphospha-3-arsapentadienide Anion and Related Compounds - Theoretical and Experimental Investigations”. European Journal of Inorganic Chemistry 2012.15 (2012): 2502-2507.