Structural,Spectroscopic and Computational Examination of the Dative Interaction in Constrained Phosphine–Stibines and Phosphine–Stiboranes |
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Authors: | Brian A. Chalmers Prof. Michael Bühl Dr. Kasun S. Athukorala Arachchige Prof. Alexandra M. Z. Slawin Dr. Petr Kilian |
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Affiliation: | EaStChem School of Chemistry, University of St. Andrews, St. Andrews, Fife KY16 9ST (UK) |
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Abstract: | A series of phosphine–stibine and phosphine–stiborane peri‐substituted acenaphthenes containing all permutations of pentavalent groups ?SbClnPh4–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 ?SbCl2Ph2 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 SbIII 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 σ4P→σ6Sb structural motif. |
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Keywords: | antimony dative bond donor– acceptor systems phosphorus synthesis |
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