Mesityltellurenyl cations stabilized by triphenylpnictogens [MesTe(EPh₃)] + (E = P, As, Sb)

Beckmann, Jens, Bolsinger, Jens, Duthie, Andrew, Finke, Pamela, Lork, Enno, Ludtke, Carsten, Mallow, Ole and Mebs, Stefan 2012, Mesityltellurenyl cations stabilized by triphenylpnictogens [MesTe(EPh₃)] + (E = P, As, Sb), Inorganic chemistry, vol. 51, no. 22, pp. 12395-12406, doi: 10.1021/ic3017722.

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Title Mesityltellurenyl cations stabilized by triphenylpnictogens [MesTe(EPh₃)] + (E = P, As, Sb)
Formatted title Mesityltellurenyl cations stabilized by triphenylpnictogens [MesTe(EPh₃)] + (E = P, As, Sb)
Author(s) Beckmann, Jens
Bolsinger, Jens
Duthie, Andrew
Finke, Pamela
Lork, Enno
Ludtke, Carsten
Mallow, Ole
Mebs, Stefan
Journal name Inorganic chemistry
Volume number 51
Issue number 22
Start page 12395
End page 12406
Total pages 12
Publisher American Chemical Society
Place of publication Washington, D.C.
Publication date 2012
ISSN 0020-1669
Summary 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]− (4b). In the reaction with Ph₃Bi, the crude product contained the cation [MesTe(BiPh₃)]+ (5a) and the anion [Ph₂Bi(O₃SCF₃)₂]− (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 2–4 were also obtained by the one-pot reaction of Mes₂Te, Ph₃E (E = P, As, Sb) and HO₃SCF₃. Compounds 1–4 and 6 were investigated by single-crystal X-ray diffraction. The molecular structures of 1a–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.
Language eng
DOI 10.1021/ic3017722
Field of Research 039904 Organometallic Chemistry
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1 Refereed article in a scholarly journal
Copyright notice ©2012, American Chemical Society
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Document type: Journal Article
Collection: School of Life and Environmental Sciences
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