School of Chemistry, University of St. Andrews, St. Andrews, Fife, United Kingdom, KY16 9ST.
Inorg Chem. 2010 Aug 16;49(16):7577-96. doi: 10.1021/ic101086h.
A range of structurally diverse compounds 1-15 {NapSPh.Br(4) (Nap = naphthalene-1,8-diyl); Nap[SePh][EPh].Br(4) (E = Se, S); NapSePh.I(2); Nap[SePh][EPh].3/2I(2) (E = Se, S); Nap[TePh][G].X(2) (G = SePh, SPh, Br, I; X = Br, I); and Nap(PPh(2)OH)(SPh)Br(3)(-)} 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[PPh(2)][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-ER(2)-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-ER(2), 8-E-3) adducts are formed. Upon treatment with dibromine, selenium donor compounds D2 {NapSePh} 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 I(2) 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.
一系列结构多样的化合物 1-15，由取代基位于萘环间位的供体 D1-D8 {Nap[ER][E'R]（ER/E'R = SPh，SePh，TePh）；Nap[TePh][X]（X = Br，I）；和 Nap[PPh(2)][SPh]}与二溴和二碘反应形成，经 X 射线晶体学和可能的多核 NMR、IR 和 MS 进行了表征。1-15 的 X 射线数据通过萘环扭转、对位原子位移、张开角大小、对位距离、芳环取向和准线性三体排列进行了分析。高价线性部分在电荷转移模型和 Pimentel 和 Rundle 引入的 3c-4e 模型的背景下进行了考虑。一般来说，最终产物的构象符合基于电荷转移的规则，即当卤素（X）比硫属元素（E）更具电负性时，会产生“跷跷板”（X-ER(2)-X，10-E-4）加合物，如果情况相反，则会形成 CT“辐条”（X-X-ER(2)，8-E-3）加合物。与二溴反应时，硒供体化合物 D2 {NapSePh}和 D3 {Nap[SePh][SPh]}生成含有高价 X-E...E' 3c-4e 型相互作用的溴代硒酰阳离子的三溴化物盐。与二碘反应时，D2 和 D3 形成“Z 形”、“扩展辐条”加合物，其中含有不常见的 2:3 供体/硫属元素比，并包含由罕见的 I...I 相互作用结合在一起的 I(2)链。如预期的那样，与二卤化物反应后，Te 供体 D4-D7 {Nap[TePh][X]（X = Br，I）；Nap[TePh][EPh]（E = Se，S）}形成“跷跷板”10-E-4 加合物。一般来说，萘环的扭曲在各自的供体化合物和产物 1-15 之间是相当的。离子物种 2 和 3 显示出分子扭曲的明显减少，这可以通过弱对位相互作用缓解空间应变和开始的 3c-4e 键合来解释。
