{"title":"The curious case of co-planarity in di-nuclear triel complexes: a density functional investigation†","authors":"Mayank Khera and Neetu Goel","doi":"10.1039/D4DT02453B","DOIUrl":null,"url":null,"abstract":"<p >Density functional investigation of intramolecular triel (Tr) bonding present in di-nuclear aryl complexes of group 13 elements having general formula [(Tr)Me<small><sub>2</sub></small>(2,6-(X)<small><sub>2</sub></small>C<small><sub>6</sub></small>H<small><sub>3</sub></small>O)]<small><sub>2</sub></small> (Tr = B, Al, Ga, In & Tl and X = OMe, OEt, OH, OPh, NH<small><sub>2</sub></small>, SH, Cl, F) has been performed. Conclusive evidence of the concurrent two σ-hole interaction has been provided by analysis of the Tr bond length, interaction energy (Δ<em>E</em>), second order perturbation energy (<em>E</em><small><sup>2</sup></small>), charge transfer (Δ<em>q</em>), quantum theory of atom in molecules (QTAIM) and noncovalent interaction (NCI) plots for 12 complexes. The Tr bond length in the optimized geometry varies from 2.49 to 2.89 Å in Al complexes (<strong>1–8</strong>) and 2.66 to 2.83 Å in other group 13 element complexes (<strong>9–12</strong>) at the PBE0-D3 functional. The interaction energy calculation reveals that the co-planar structure of complexes containing Al (<strong>1–8</strong>) are more stable than their rotamers by 8–15 kcal mol<small><sup>−1</sup></small>, whereas the di-nuclear complexes of other group 13 complexes (<strong>9–12</strong>) orient in a non-planar pocket structure. This loss of co-planarity reveals the fact that its presence relies on the Tr atom, not the intramolecular Tr bonding, which has a striking impact on the crystal engineering of di-nuclear complexes of Group 13.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 2","pages":" 851-862"},"PeriodicalIF":3.5000,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/dt/d4dt02453b","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Density functional investigation of intramolecular triel (Tr) bonding present in di-nuclear aryl complexes of group 13 elements having general formula [(Tr)Me2(2,6-(X)2C6H3O)]2 (Tr = B, Al, Ga, In & Tl and X = OMe, OEt, OH, OPh, NH2, SH, Cl, F) has been performed. Conclusive evidence of the concurrent two σ-hole interaction has been provided by analysis of the Tr bond length, interaction energy (ΔE), second order perturbation energy (E2), charge transfer (Δq), quantum theory of atom in molecules (QTAIM) and noncovalent interaction (NCI) plots for 12 complexes. The Tr bond length in the optimized geometry varies from 2.49 to 2.89 Å in Al complexes (1–8) and 2.66 to 2.83 Å in other group 13 element complexes (9–12) at the PBE0-D3 functional. The interaction energy calculation reveals that the co-planar structure of complexes containing Al (1–8) are more stable than their rotamers by 8–15 kcal mol−1, whereas the di-nuclear complexes of other group 13 complexes (9–12) orient in a non-planar pocket structure. This loss of co-planarity reveals the fact that its presence relies on the Tr atom, not the intramolecular Tr bonding, which has a striking impact on the crystal engineering of di-nuclear complexes of Group 13.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.