Mesityltellurenyl Cations Stabilized by Triphenylpnictogens [MesTe(EPh3)]+ (E = P, As, Sb)

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• 作者：Jens Beckmann ; Jens Bolsinger ; Andrew Duthie ; Pamela Finke ; Enno Lork ; Carsten L眉dtke ; Ole Mallow ; Stefan Mebs
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：November 19, 2012
• 年：2012
• 卷：51
• 期：22
• 页码：12395-12406
• 全文大小：548K
• 年卷期：v.51,no.22(November 19, 2012)
• ISSN：1520-510X

文摘

The homoleptic 1:1 Lewis pair (LP) complex [MesTe(TeMes₂)]O₃SCF₃ (1) featuring the cation [MesTe(TeMes₂)]⁺ (1a) was obtained by the reaction of Mes₂Te with HO₃SCF₃. The reaction of 1 with Ph₃E (E = P, As, Sb, Bi) proceeded with substitution of Mes₂Te and provided the heteroleptic 1:1 LP complexes [MesTe(EPh₃)]O₃SCF₃ (2, E = P; 3, E = As) and [MesTe(SbPh₃)][Ph₂Sb(O₃SCF₃)₂] (4) featuring the cations [MesTe(EPh₃)]⁺ (2a, E = P; 3a, E = As; 4a, E = Sb) and the anion [Ph₂Sb(O₃SCF₃)₂]^{鈭?/sup> (4b). In the reaction with Ph₃Bi, the crude product contained the cation [MesTe(BiPh₃)]+ (5a) and the anion [Ph₂Bi(O₃SCF₃)₂]鈭?/sup> (5b); however, the heteroleptic 1:1 LP complex [MesTe(BiPh₃)][Ph₂Bi(O₃SCF₃)₂] (5) could not be isolated because of its limited stability. Instead, fractional crystallization furnished a large amount of Ph₂BiO₃SCF₃ (6), which was also obtained by the reaction of Ph₃Bi with HO₃SCF₃. The formation of the anions 4b and 5b involves a phenyl group migration from Ph₃E (E = Sb, Bi) to the MesTe+ cation and afforded MesTePh as the byproduct, which was identified in the mother liquor. The heteroleptic 1:1 LP complexes 2鈥?b>4 were also obtained by the one-pot reaction of Mes₂Te, Ph₃E (E = P, As, Sb) and HO₃SCF₃. Compounds 1鈥?b>4 and 6 were investigated by single-crystal X-ray diffraction. The molecular structures of 1a鈥?b>4a were used for density functional theory calculations at the B3PW91/TZ level of theory and studied using natural bond order (NBO) analyses as well as real-space bonding descriptors derived from an atoms-in-molecules (AIM) analysis of the theoretically obtained electron density. Additionally, the electron localizability indicator (ELI-D) and the delocalization index are derived from the corresponding pair density.}