{"title":"用MO， NBO和QTAIM分析计算了铂及其相关物质的η - 3-丙炔配合物的键合","authors":"John P. Graham","doi":"10.1007/s11224-025-02521-7","DOIUrl":null,"url":null,"abstract":"<div><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></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 5","pages":"1577 - 1584"},"PeriodicalIF":2.2000,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11224-025-02521-7.pdf","citationCount":"0","resultStr":"{\"title\":\"Computational study of the bonding in η3-propargyl complexes of platinum and related species using MO, NBO, and QTAIM analysis\",\"authors\":\"John P. Graham\",\"doi\":\"10.1007/s11224-025-02521-7\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><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></div>\",\"PeriodicalId\":780,\"journal\":{\"name\":\"Structural Chemistry\",\"volume\":\"36 5\",\"pages\":\"1577 - 1584\"},\"PeriodicalIF\":2.2000,\"publicationDate\":\"2025-06-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://link.springer.com/content/pdf/10.1007/s11224-025-02521-7.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Structural Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s11224-025-02521-7\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Structural Chemistry","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s11224-025-02521-7","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Computational study of the bonding in η3-propargyl complexes of platinum and related species using MO, NBO, and QTAIM analysis
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.
期刊介绍：
Structural Chemistry is an international forum for the publication of peer-reviewed original research papers that cover the condensed and gaseous states of matter and involve numerous techniques for the determination of structure and energetics, their results, and the conclusions derived from these studies. The journal overcomes the unnatural separation in the current literature among the areas of structure determination, energetics, and applications, as well as builds a bridge to other chemical disciplines. Ist comprehensive coverage encompasses broad discussion of results, observation of relationships among various properties, and the description and application of structure and energy information in all domains of chemistry.
We welcome the broadest range of accounts of research in structural chemistry involving the discussion of methodologies and structures,experimental, theoretical, and computational, and their combinations. We encourage discussions of structural information collected for their chemicaland biological significance.
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