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dc.contributor.authorKnight, Fergus Ross
dc.contributor.authorFuller, Amy
dc.contributor.authorBuehl, Michael
dc.contributor.authorSlawin, Alexandra Martha Zoya
dc.contributor.authorWoollins, J Derek
dc.date.accessioned2011-07-14T23:05:11Z
dc.date.available2011-07-14T23:05:11Z
dc.date.issued2010-08-16
dc.identifier.citationKnight , F R , Fuller , A , Buehl , M , Slawin , A M Z & Woollins , J D 2010 , ' Hypervalent adducts of chalcogen-containing peri -substituted naphthalenes; reactions of sulfur, selenium, and tellurium with dihalogens ' Inorganic Chemistry , vol. 49 , no. 16 , pp. 7577-7596 . https://doi.org/10.1021/ic101086hen
dc.identifier.issn0020-1669
dc.identifier.otherPURE: 2038271
dc.identifier.otherPURE UUID: e83feb6a-8ccc-46d5-b0d8-74fb02018b6a
dc.identifier.otherWOS: 000280582900044
dc.identifier.otherScopus: 77955491432
dc.identifier.otherORCID: /0000-0002-1095-7143/work/48131757
dc.identifier.otherORCID: /0000-0002-9527-6418/work/56861817
dc.identifier.otherORCID: /0000-0002-1498-9652/work/31779246
dc.identifier.urihttp://hdl.handle.net/10023/1918
dc.descriptionThe work in this project was supported by the Engineering and Physical Sciences Research Council (EPSRC)en
dc.description.abstractA range of structurally diverse compounds 1-15 {Nap[SPh]2•Br4 (Nap = naphthalene-1,8-diyl); Nap[SePh][EPh]•Br4 (E = Se, S); Nap[SePh]2•I2; Nap[SePh][EPh]•3/2I2 (E = Se, S); Nap[TePh][G]•X2 (G = SePh, SPh, Br, I; X = Br, I); and [Nap(PPh2OH)(SPh)]+Br3-} formed from the reactions between peri-substituted naphthalene chalcogen donors D1-D8 {Nap[ER][E0R] (ER/E0R = SPh, SePh, TePh); Nap[TePh][X] (X = Br, I); and Nap[PPh2][SPh]} and dibromine and diiodine were characterized by X-ray crystallography and where possible by multinuclear NMR, IR, and MS. X-ray data for 1-15 were analyzed by naphthalene ring torsions, peri-atom displacement, splay angle magnitude, peri-distance, aromatic ring orientations, and quasi-linear three-body arrangements. The hypervalent linear moieties are considered in the context of the charge-transfer model and the 3c-4e model introduced by Pimentel and Rundle. In general, the conformation of the final products obeyed the rule based on charge-transfer that “seesaw” (X-ER2-X, 10-E-4) adducts arise when the halogen (X) is more electronegative than the chalcogen (E), and if the converse is true then, CT “spoke” (X-X-ER2, 8-E-3) adducts are formed. Upon treatment with dibromine, selenium donor compounds D2 {Nap[SePh]2} and D3 {Nap[SePh][SPh]} afford unusual tribromide salts of bromoselenyl cations containing a hypervalent X-E---E` 3c-4e type interaction. Upon treatment with diiodine, D2 and D3 form “Z-shaped”, “extended spoke” adducts containing an uncommon 2:3 donor/chalcogen ratio and incorporating chains of I2 held together by rare I---I interactions. As expected, “seesaw” 10-E-4 adducts are formed following the reaction of Te donors D4-D7 {Nap[TePh][X] (X = Br, I); Nap[TePh][EPh] (E = Se, S)} with the dihalogens. Naphthalene distortion in general is comparable between respective donor compounds and products 1-15. Ionic species 2 and 3 display a noticeable reduction in molecular distortion explained by the relief of steric strain via weak peri-interactions and the onset of 3c-4e bonding.
dc.format.extent20
dc.language.isoeng
dc.relation.ispartofInorganic Chemistryen
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see DOI: 10.1021/ic101086hen
dc.subjectQD Chemistryen
dc.subject.lccQDen
dc.titleHypervalent adducts of chalcogen-containing peri-substituted naphthalenes; reactions of sulfur, selenium, and tellurium with dihalogensen
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/10.1021/ic101086h
dc.description.statusPeer revieweden
dc.date.embargoedUntil2011-07-15
dc.identifier.urlhttp://www.scopus.com/inward/record.url?scp=77955491432&partnerID=8YFLogxKen


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