Exploring the Role of Strong Intramolecular Coordination of the 2-(2'-pyridyl)phenyl Group in Heavy Main Group Halides: Insights from Synthesis, Structural, and Bonding Analyses

Rajesh Deka, Arup Sarkar, Anand Gupta, Ray J. Butcher, Peter C. Junk, David R. Turner, Glen B. Deacon, Harkesh B. Singh

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By the transmetallation of ppyHgCl [ppy = 2-(2'-pyridyl)phenyl] (1) with SnCl4 and SbCl3, the synthesis of the monoorgano main group halides, [ppySnCl3(H2O)]·2(0.5diox) (diox = 1,4-dioxane) [2(H2O)]·2(0.5diox) and [ppySbCl2] (3) was achieved. The reaction of 1 with BiCl3 does not give the analogous monoorganobismuth dichloride. Instead, it results in the formation of [(ppy)2Bi]+·[ppyBiCl3] (4). Reactions of (ppy)2Te and (ppyTe)2 with SO2Cl2 and Br2 result in the formation of ppyTeCl (5) and ppyTeBr (6) respectively. All the synthesized compounds were characterized by multi-nuclear NMR spectroscopy (1H, 13C, 119Sn, and 125Te), FT-IR spectroscopy, ESI-MS, CHN analysis, and single-crystal X-ray diffraction studies. The molecular structures of 2–6 reveal strong intramolecular coordination of the N-atoms of the pendant arms with the main group element centers. DFT calculations; including Natural Bond Order (NBO), Electron Localization Function (ELF), Electrostatic Surface Potential (ESP) and Atoms in Molecules (AIM) infer that the stability of 2–6 relies on the σ-hole participation of the element center with the N-lone pair of the pyridyl arm.

Original languageEnglish
Pages (from-to)2143-2152
Number of pages10
JournalEuropean Journal of Inorganic Chemistry
Issue number22
Publication statusPublished - 16 Jun 2020


  • Density functional calculations
  • Halides
  • Intramolecular interactions
  • Main group elements
  • Structure elucidation
  • Transmetallation

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