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dc.contributor.authorChalmers, Brian Alexander
dc.contributor.authorBuehl, Michael
dc.contributor.authorAthukorala Arachchige, Kasun Sankalpa
dc.contributor.authorSlawin, Alexandra Martha Zoya
dc.contributor.authorKilian, Petr
dc.date.accessioned2016-03-28T11:02:56Z
dc.date.available2016-03-28T11:02:56Z
dc.date.issued2015-05-11
dc.identifier.citationChalmers , 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 . https://doi.org/10.1002/chem.201500281en
dc.identifier.issn0947-6539
dc.identifier.otherPURE: 170647762
dc.identifier.otherPURE UUID: dde1d125-30ec-4212-8899-c095caa6d125
dc.identifier.otherScopus: 84928731420
dc.identifier.otherORCID: /0000-0002-1095-7143/work/48131742
dc.identifier.otherORCID: /0000-0002-2999-2272/work/55901238
dc.identifier.otherORCID: /0000-0002-9527-6418/work/56862112
dc.identifier.otherORCID: /0000-0001-6379-3026/work/58285425
dc.identifier.otherWOS: 000354027300031
dc.identifier.urihttp://hdl.handle.net/10023/8495
dc.descriptionThis work was financially supported by the EPSRC and COST actions CM0802 PhoSciNet and CM1302 SIPs.en
dc.description.abstractA 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.
dc.language.isoeng
dc.relation.ispartofChemistry - A European Journalen
dc.rights© 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/abstracten
dc.subjectAntimonyen
dc.subjectDative bonden
dc.subjectDonor–acceptor systemsen
dc.subjectPhosphorusen
dc.subjectSynthesisen
dc.subjectQD Chemistryen
dc.subjectDASen
dc.subject.lccQDen
dc.titleA structural, spectroscopic and computational examination of the dative interaction in constrained phosphine–stibines and phosphine–stiboranesen
dc.typeJournal articleen
dc.description.versionPostprinten
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.identifier.doihttps://doi.org/10.1002/chem.201500281
dc.description.statusPeer revieweden
dc.date.embargoedUntil2016-03-27
dc.identifier.urlhttp://onlinelibrary.wiley.com/doi/10.1002/chem.201500281/suppinfoen


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