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Title: Hypervalent adducts of chalcogen-containing peri-substituted naphthalenes; reactions of sulfur, selenium, and tellurium with dihalogens
Authors: Knight, Fergus Ross
Fuller, Amy
Buehl, Michael
Slawin, Alexandra Martha Zoya
Woollins, J Derek
Keywords: QD Chemistry
Issue Date: 16-Aug-2010
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 . , 10.1021/ic101086h
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.
Version: Postprint
Description: The work in this project was supported by the Engineering and Physical Sciences Research Council (EPSRC)
Status: Peer reviewed
ISSN: 0020-1669
Type: Journal article
Rights: This 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/ic101086h
Appears in Collections:University of St Andrews Research
Chemistry Research

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