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Hypervalent adducts of chalcogen-containing peri-substituted naphthalenes; reactions of sulfur, selenium, and tellurium with dihalogens
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dc.contributor.author | Knight, Fergus Ross | |
dc.contributor.author | Fuller, Amy | |
dc.contributor.author | Buehl, Michael | |
dc.contributor.author | Slawin, Alexandra Martha Zoya | |
dc.contributor.author | Woollins, J Derek | |
dc.date.accessioned | 2011-07-14T23:05:11Z | |
dc.date.available | 2011-07-14T23:05:11Z | |
dc.date.issued | 2010-08-16 | |
dc.identifier | 2038271 | |
dc.identifier | e83feb6a-8ccc-46d5-b0d8-74fb02018b6a | |
dc.identifier | 000280582900044 | |
dc.identifier | 77955491432 | |
dc.identifier.citation | Knight , 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/ic101086h | en |
dc.identifier.issn | 0020-1669 | |
dc.identifier.other | ORCID: /0000-0002-1095-7143/work/48131757 | |
dc.identifier.other | ORCID: /0000-0002-9527-6418/work/56861817 | |
dc.identifier.other | ORCID: /0000-0002-1498-9652/work/31779246 | |
dc.identifier.uri | https://hdl.handle.net/10023/1918 | |
dc.description | The work in this project was supported by the Engineering and Physical Sciences Research Council (EPSRC) | en |
dc.description.abstract | A 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.extent | 20 | |
dc.format.extent | 1378771 | |
dc.language.iso | eng | |
dc.relation.ispartof | Inorganic Chemistry | en |
dc.subject | QD Chemistry | en |
dc.subject.lcc | QD | en |
dc.title | Hypervalent adducts of chalcogen-containing peri-substituted naphthalenes; reactions of sulfur, selenium, and tellurium with dihalogens | en |
dc.type | Journal article | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.contributor.institution | University of St Andrews. EaSTCHEM | en |
dc.identifier.doi | 10.1021/ic101086h | |
dc.description.status | Peer reviewed | en |
dc.date.embargoedUntil | 2011-07-15 | |
dc.identifier.url | http://www.scopus.com/inward/record.url?scp=77955491432&partnerID=8YFLogxK | en |
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