Evaluation of structural, spectroscopic, bonding and electronic properties of some organotin(IV)-phosphoric triamide complexes by using help of DFT, QTAIM and Hirshfeld surface investigations
[Display omitted] •Organotin(IV)-phosphoric triamide complexes including iphosphoric triamide ligand with a segment (O═)P[N]3) are explored to investigate various properties by means of the DFT calculations.•The connectivities around tin center, especially Sn…O(═P) contact, in such complexes are ful...
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Veröffentlicht in: | COMPUTATIONAL AND THEORETICAL CHEMISTRY 2021-01, Vol.1195, p.113098, Article 113098 |
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Sprache: | eng |
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•Organotin(IV)-phosphoric triamide complexes including iphosphoric triamide ligand with a segment (O═)P[N]3) are explored to investigate various properties by means of the DFT calculations.•The connectivities around tin center, especially Sn…O(═P) contact, in such complexes are fully analyzed by QTAIM method.•Intermolecular interactions in the crystal structures are studied by using Hirshfeld surface analysis.
Different computational investigations by using help of DFT (density functional theory), QTAIM (quantum theory of atom in molecule) and HS (Hirshfeld surface) approaches are carried out to evaluate the various properties, especially Sn…O interactions, of some organotin(IV)-phosphoric triamide (OP is introduced as the phosphoric triamide ligand with a segment (O═)P[N]3) complexes. Among the most important results of this study is the absence of a net Sn-O bond between Sn(IV) center and O atom of P═O group (of OP ligand) in the segment Sn(CH3)2Cl2(OP)2, where no bond critical point (BCP) is found along the path connecting tin and oxygen atoms. However, a survey of other connectivities (such as Sn…C and C/Cl…O contacts) suggests a weak non-covalent interaction (with ionic in nature) for Sn…O(═P) in the studied complexes. DFT studies show that orientation of OP ligands around tin (trans or cis) is important for the strength of Sn…O interactions; so that a slightly higher strength is found in trans(OP)-form six-coordinate complexes of 1 – 3. Furthermore, a precise exploration of the intermolecular interactions by using Hirshfeld surface analysis reveals that the H…O/O…H (for 1 – 4) and H…Cl/Cl…H (for 1 – 5) contacts are favoured. A characteristic Sn….Cl contact with a high enrichment ratio is explored in five-coordinate complex 5. Finally, the presence of normal intermolecular interactions in the crystal structures of 3 and 4 is aligned with the lower chemical reactivities of these structures. |
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ISSN: | 2210-271X 1872-7999 |
DOI: | 10.1016/j.comptc.2020.113098 |