An insight into triel bonds in O, O′-diarylphosphorodithioates of thallium(i): experimental and theoretical investigations. (14th December 2021)

• Record Type: Journal Article
• Authors: Firdoos, Tahira; Kumar, Pretam; Radha, Anu; Gomila, Rosa M.; Frontera, Antonio; Sood, Puneet; Pandey, Sushil K.
• Is Part Of: New journal of chemistry. Volume 46:Number 2(2022)
• Page Start: 832
• Page End: 843
• Publication Date: 2021-12-14
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/d1nj04852j
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : Two new thallium(i ) compounds have been synthesized and structurally characterized. The existence of triel bonds in these compounds has been confirmed by HSA and DFT calculations using QTAIM and NCI plot index methods. Abstract : The vital role of triel bonding (TrB) has been highlighted in two new thallium compounds i.e. Tl + [{(4-C2 H5 )C6 H4 O}2 PS2 ]2 − (1 ) and Tl[{(4-CH(CH3 )2 )C6 H4 O}2 PS2 ]2 (2 ). These new compounds have been characterized by elemental and spectral analyses. The crystal structures of 1 and 2 belong to the monoclinic and triclinic systems with space groups P 21/ c and P 1̄, respectively. Interestingly, compound 1 exists in ionic form and is stabilized through intramolecular Tl⋯S (TrBs) interactions wherein the thallium atom is symmetrically positioned in the cleft of the ligand with longer Tl–S distances. In compound 2, the thallium atom is coordinated to one sulfur atom and the other sulfur atom participates in TrB interaction. Both compounds also exhibit intermolecular Tl⋯S, Tl⋯π (TrBs), and C–H⋯Tl (anagostic) interactions, which assist to form unique supramolecular architectures owing to large size as well as coordinative unsaturation on the thallium. These non-covalent TrB interactions were authenticated by Hirshfeld surface analysis (HSA) and density functional theory (DFT) calculations using the quantum theory of atoms-in-molecules (QTAIM) and non-covalent interaction plot (NCI Plot) index methods. TrBs involving Tl have been scarcely described in the literature; therefore this work provides valuable insight into the importance of these unprecedented TrBs in the solid state.