A structural, spectroscopic and computational examination of the dative interaction in constrained phosphine–stibines and phosphine–stiboranes
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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 including single crystal diffraction and multinuclear NMR. 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, consistent with a change from a bonding to a non-bonding interaction in a response to relatively small change 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 σ4P→σ6Sb structural motif.
Chalmers , B A , Buehl , M , Athukorala Arachchige , K S , Slawin , A M Z & Kilian , P 2015 , ' A structural, spectroscopic and computational examination of the dative interaction in constrained phosphine–stibines and phosphine–stiboranes ' Chemistry - A European Journal , vol 21 , no. 20 , pp. 7520-7531 . DOI: 10.1002/chem.201500281
Chemistry - A European Journal
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This is the accepted version of the following article: Chalmers, B. A., Bühl, M., Athukorala Arachchige, K. S., Slawin, A. M. Z. and Kilian, P. (2015), Structural, Spectroscopic and Computational Examination of the Dative Interaction in Constrained Phosphine–Stibines and Phosphine–Stiboranes. Chem. Eur. J., which has been published in final form at http://onlinelibrary.wiley.com/doi/10.1002/chem.201500281/abstract
This work was financially supported by the EPSRC and COST actions CM0802 PhoSciNet and CM1302 SIPs.
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