Hypervalent Adducts of Chalcogen-Containing <i>peri</i>-Substituted Naphthalenes; Reactions of Sulfur, Selenium, and Tellurium with Dihalogens

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][E′R] (ER/E′R = 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.