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<p>Density functional theoretical calculations are used to investigate the nature of the metal–ligand bonding in the η<sup>3</sup>-propargyl complexes of Pt(II) and related species. Of particular interest are the interactions between the central propargyl C atom and the Pt centre. Experimental data has shown that the distance between Pt and the central C atom is the shortest Pt-C bond in the η<sup>3</sup>-propargyl complex [(η<sup>3</sup>-PhCCCH<sub>2</sub>)Pt(PPh<sub>3</sub>)<sub>2</sub>]<sup>+</sup>, suggesting a strong bonding interaction. However, approximate molecular orbital calculations have suggested that bonding between Pt and the propargyl ligand occurs primarily through the terminal propargyl C atoms. In this contribution, Pt-C interactions are analysed using molecular orbital theory, natural bonding orbital analysis, and the quantum theory of atoms in molecules (QTAIM). Calculated bond orders and delocalization indices suggest that there is a significant bonding interaction between the Pt centre and central carbon atom, but that this interaction is much weaker than the short bond distance would suggest. Energy decomposition using the interacting quantum atoms (IQA) approach further supports this conclusion. A comparison is made to the bonding in related model metallacyclobutene and η<sup>3</sup>-allyl complexes.</p>

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Computational study of the bonding in η3-propargyl complexes of platinum and related species using MO, NBO, and QTAIM analysis

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  • 发表日期：

    2025年6月10日

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  • John P. Graham

摘要

Density functional theoretical calculations are used to investigate the nature of the metal–ligand bonding in the η3-propargyl complexes of Pt(II) and related species. Of particular interest are the interactions between the central propargyl C atom and the Pt centre. Experimental data has shown that the distance between Pt and the central C atom is the shortest Pt-C bond in the η3-propargyl complex [(η3-PhCCCH2)Pt(PPh3)2]+, suggesting a strong bonding interaction. However, approximate molecular orbital calculations have suggested that bonding between Pt and the propargyl ligand occurs primarily through the terminal propargyl C atoms. In this contribution, Pt-C interactions are analysed using molecular orbital theory, natural bonding orbital analysis, and the quantum theory of atoms in molecules (QTAIM). Calculated bond orders and delocalization indices suggest that there is a significant bonding interaction between the Pt centre and central carbon atom, but that this interaction is much weaker than the short bond distance would suggest. Energy decomposition using the interacting quantum atoms (IQA) approach further supports this conclusion. A comparison is made to the bonding in related model metallacyclobutene and η3-allyl complexes.