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dc.contributor.authorAthukorala Arachchige, K.S.
dc.contributor.authorDiamond, L.M.
dc.contributor.authorKnight, F.R.
dc.contributor.authorLechner, M.-L.
dc.contributor.authorSlawin, A.M.Z.
dc.contributor.authorWoollins, J.D.
dc.identifier.citationAthukorala Arachchige , K S , Diamond , L M , Knight , F R , Lechner , M-L , Slawin , A M Z & Woollins , J D 2014 , ' Synthetic, structural, and spectroscopic studies of sterically crowded tin-chalcogen acenaphthenes ' , Organometallics , vol. 33 , no. 21 , pp. 6089-6102 .
dc.identifier.otherPURE: 158739995
dc.identifier.otherPURE UUID: 112bdfbf-28b6-4885-9f98-f5b3397dd789
dc.identifier.otherScopus: 84909992178
dc.identifier.otherORCID: /0000-0002-9527-6418/work/56861992
dc.identifier.otherORCID: /0000-0002-1498-9652/work/31779190
dc.identifier.otherWOS: 000344722000028
dc.descriptionThe work in this project was supported by the Engineering and Physical Sciences Research Council (EPSRC) and EaStCHEM.en
dc.description.abstractA series of sterically encumbered peri-substituted acenaphthenes have been prepared containing chalcogen and tin moieties at the close 5,6-positions (Acenap[SnPh3][ER], Acenap = acenaphthene-5,6-diyl, ER = SPh (1), SePh (2), TePh (3), SEt (4); Acenap[SnPh2Cl][EPh], E = S (5), Se (6); Acenap[SnBu2Cl][ER], ER = SPh(7), SePh (8), SEt (9)). Two geminally bis(peri-substituted) derivatives ({Acenap[SPh2]}2SnX2, X = Cl (10), Ph (11)) have also been prepared, along with the bromo–sulfur derivative Acenap(Br)(SEt) (15). All 11 chalcogen–tin compounds align a Sn–CPh/Sn–Cl bond along the mean acenaphthene plane and position a chalcogen lone pair in close proximity to the electropositive tin center, promoting the formation of a weakly attractive intramolecular donor–acceptor E···Sn–CPh/E···Sn–Cl 3c-4e type interaction. The extent of E→Sn bonding was investigated by X-ray crystallography and solution-state NMR and was found to be more prevalent in triorganotin chlorides 5–9 in comparison with triphenyltin derivatives 1–4. The increased Lewis acidity of the tin center resulting from coordination of a highly electronegative chlorine atom was found to greatly enhance the lp(E)−σ*(Sn–Y) donor–acceptor 3c-4e type interaction, with substantially shorter E–Sn peri distances observed in the solid state for triorganotin chlorides 5–9 (∼75% ∑rvdW) and significant 1J(119Sn,77Se) spin–spin coupling constants (SSCCs) observed for 6 (163 Hz) and 8 (143 Hz) in comparison to that for the triphenyltin derivative 2 (68 Hz). Similar observations were observed for geminally bis(peri-substituted) derivatives 10 and 11.
dc.rights© 2014. American Chemical Society. This is an Accepted Manuscript of an article published in Organometallics on 10/10/2014, available online:
dc.subjectQD Chemistryen
dc.titleSynthetic, structural, and spectroscopic studies of sterically crowded tin-chalcogen acenaphthenesen
dc.typeJournal articleen
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.contributor.institutionUniversity of St Andrews.Office of the Principalen
dc.description.statusPeer revieweden

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