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

Deka, Rajesh, Sarkar, Arup, Gupta, Anand, Butcher, Ray J., Junk, Peter C., Turner, David R., Deacon, Glen B., and Singh, Harkesh B. (2020) 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. European Journal of Inorganic Chemistry, 2020 (22). pp. 2143-2152.

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Abstract

By the transmetallation of ppyHgCl [ppy = 2-(2'-pyridyl)phenyl] (1) with SnCl4 and SbCl3, the synthesis of the monoorgano main group halides, [ppySnCl(3)(H2O)]center dot 2(0.5diox) (diox = 1,4-dioxane) [2(H2O)]center dot 2(0.5diox) and [ppySbCl(2)] (3) was achieved. The reaction of 1 with BiCl3 does not give the analogous monoorganobismuth dichloride. Instead, it results in the formation of [(ppy)(2)Bi](+)center dot[ppyBiCl(3)](-) (4). Reactions of (ppy)(2)Te and (ppyTe)(2) with SO2Cl2 and Br-2 result in the formation of ppyTeCl (5) and ppyTeBr (6) respectively. All the synthesized compounds were characterized by multi-nuclear NMR spectroscopy (H-1, C-13, Sn-119, and Te-125), 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 sigma-hole participation of the element center with the N-lone pair of the pyridyl arm.

Item ID: 63419
Item Type: Article (Research - C1)
ISSN: 1099-0682
Keywords: Intramolecular interactions, Main group elements, Halides, Transmetallation, Structure elucidation, Density functional calculations
Copyright Information: © 2020 Wiley-VCH Verlag GmbH & Co.
Funders: Department of Science and Techology, India (DST), Australian Research Council (ARC), ITB-Monash Research Academy
Projects and Grants: DST Bose Fellowship 15DSTFLS00, DST Grant No. RD/0115-DSTFLS80-00, ARC DP1090100798
Date Deposited: 10 Jun 2020 07:42
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030204 Main Group Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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