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

Abstract

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.

Implementing the Ambiphilicity of an Organotellurenyl Cation for the Synthesis of a Platinum(II)‐Based Carboxylate‐Bridged Heterobimetallic Complex: Structure and Bonding Analysis

“…Starting material ppyTeCl, 5 was synthesized by the reaction of ppy 2 Te with SO 2 Cl 2 as previously reported. [14] When ppyTeCl was treated with AgClO 4 in dichloromethane solution at ambient temperature, the reaction resulted in the precipitation of silver chloride. The precipitate was filtered off and the resultant filtrate was concentrated in vacuo to afford [6] • ClO 4 (Scheme 2).…”

Charge Makes a Difference: Molecular Ionic Bismuth Compounds

“…A straightforward, and at the same time the most common, route to mono-and dianionic bismuth-(III) compounds is the adduct formation between a sufficiently Lewis acidic bismuth compound (typically BiRX 2 , BiR 2 X, or Bi(OR) 3 ; R = alkyl, aryl; X = halide) and a nucleophile X À or (OR) À (Scheme 3a). [65][66][67][68][69][70][71][72][73] Adduct formations of this type have also been observed as a result of more complex, unforeseen ligand redistribution reactions [74,75] and degradation reactions due to over-reduction of bismuth(III) precursors. [76] An unexpected route to anionic bismuth(III) compounds has been observed for carbene adducts of bismuth halides.…”

“…Heteroleptic bismuth(III) compounds bearing one anionic hydrocarbon ligand and three halide ligands per bismuth atom show a strong tendency to realize a coordination number of five. They are either coordinated by an additional neutral ligand leading to mononuclear structures (Scheme 19b, I) [65, 75] or have dinuclear structures with two bridging halide ligands in the solid state (Scheme 19b, II) [65–67, 72, 77, 180, 184] . Square pyramidal coordination geometries around bismuth are observed with the hydrocarbon ligand(s) in the apical position(s) (and on opposite sides of the Bi 2 X 6 ‐plane in the case of the dinuclear species) [68, 185] .…”

Stabilization of unusual discrete diorganotin carboxylates using the intramolecular coordination approach: synthesis, structure, TD-DFT, and Hirshfeld surface analyses

“…The bite angle at central tin atoms is O1-Sn1-O2, 55. 25 (1)1, while other bond parameters are Sn1-C1, 2.111 (5) Å; Sn1-C13, 2.114 (5) Å; Sn1-N2, 2.502 (4) Å; Sn1-N4, 2.613 (4) Å; and Sn1-Cl1, 2.416 (1) Å.…”

“…Incorporation of the intramolecular N -Sn coordination into the organotin system provides stability to unique structural motifs and may prevent the complex from undergoing polymerization by blocking the coordination site. [25][26][27] Recently, there has been increased scientific interest in investigating the intramolecular coordination of organometallic complexes. 28 In our previous reports, several new organotin-containing structural motifs have been developed employing the intramolecular N -Sn coordination approach.…”