Structural, spectroscopic and computational examination of the dative interaction in constrained phosphine-stibines and phosphine-stiboranes.

Autor: Chalmers BA; EaStChem School of Chemistry, University of St. Andrews, St. Andrews, Fife KY16 9ST (UK)., Bühl M, Athukorala Arachchige KS, Slawin AM, Kilian P
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2015 May 11; Vol. 21 (20), pp. 7520-31. Date of Electronic Publication: 2015 Mar 27.
DOI: 10.1002/chem.201500281
Abstrakt: A series of phosphine-stibine and phosphine-stiborane peri-substituted acenaphthenes containing all permutations of pentavalent groups -SbCln Ph4-n (5-9), as well as trivalent groups -SbCl2 , -Sb(R)Cl, and -SbPh2 (2-4, R=Ph, Mes), were synthesised and fully characterised by single crystal diffraction and multinuclear NMR spectroscopy. In addition, the bonding in these species was studied by DFT computational methods. The P-Sb dative interactions in both series range from strongly bonding to non-bonding as the Lewis acidity of the Sb acceptor is decreased. In the pentavalent antimony series, a significant change in the P-Sb distance is observed between -SbClPh3 and -SbCl2 Ph2 derivatives 6 and 7, respectively, consistent with a change from a bonding to a non-bonding interaction in response to relatively small modification in Lewis acidity of the acceptor. In the Sb(III) series, two geometric forms are observed. The P-Sb bond length in the SbCl2 derivative 2 is as expected for a normal (rather than a dative) bond. Rather unexpectedly, the phosphine-stiborane complexes 5-9 represent the first examples of the σ(4) P→σ(6) Sb structural motif.
(© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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