Mechanism of the Formation of trans- and cis-Isomers of the Bis(chelate) Pd(II) and Pt(II) Complexes Based on (N,O(S,Se))-Bidentate Azomethines: A Quantum Chemical Study
{"title":"Mechanism of the Formation of trans- and cis-Isomers of the Bis(chelate) Pd(II) and Pt(II) Complexes Based on (N,O(S,Se))-Bidentate Azomethines: A Quantum Chemical Study","authors":"N. N. Kharabayev, D. V. Steglenko, V. I. Minkin","doi":"10.1134/S107032842460058X","DOIUrl":null,"url":null,"abstract":"<p>The molecular structures and relative energies of <i>trans-</i> and <i>cis-</i>isomers of bis(chelate) complexes of Pd(II) and Pt(II) salicylal-, thiosalicylal-, and selenosalicylaldiiminates are calculated using the density functional theory. The role of the kinetic factor in the formation of the <i>trans-</i> and <i>cis-</i>isomers of the PdL<sub>2</sub> and PtL<sub>2</sub> complexes is studied in the framework of the model of the step-by-step formation of the bis(ligand) metal complexes ML<sub>2</sub> (M<sup>++</sup> + (L)<sup>–</sup> → (ML)<sup>+</sup>, (ML)<sup>+</sup> + (L)<sup>–</sup>→ ML<sub>2</sub>). The competition of the <i>trans-</i> and <i>cis-</i>isomers of the PdL<sub>2</sub> and PtL<sub>2</sub> bis(chelate) azomethine complexes with the coordination nodes MN<sub>2</sub>O<sub>2</sub>, MN<sub>2</sub>S<sub>2</sub>, and MN<sub>2</sub>Se<sub>2</sub> is shown to be determined by both the energy preference of one of possible configurations and activation barriers of the isomerization of the products formed in the first step of the interaction of the initial reagents.</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":"50 10","pages":"802 - 808"},"PeriodicalIF":1.1000,"publicationDate":"2024-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Russian Journal of Coordination Chemistry","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1134/S107032842460058X","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
The molecular structures and relative energies of trans- and cis-isomers of bis(chelate) complexes of Pd(II) and Pt(II) salicylal-, thiosalicylal-, and selenosalicylaldiiminates are calculated using the density functional theory. The role of the kinetic factor in the formation of the trans- and cis-isomers of the PdL2 and PtL2 complexes is studied in the framework of the model of the step-by-step formation of the bis(ligand) metal complexes ML2 (M++ + (L)– → (ML)+, (ML)+ + (L)–→ ML2). The competition of the trans- and cis-isomers of the PdL2 and PtL2 bis(chelate) azomethine complexes with the coordination nodes MN2O2, MN2S2, and MN2Se2 is shown to be determined by both the energy preference of one of possible configurations and activation barriers of the isomerization of the products formed in the first step of the interaction of the initial reagents.
期刊介绍:
Russian Journal of Coordination Chemistry is a journal that publishes reviews, original papers, and short communications on all aspects of theoretical and experimental coordination chemistry. Modern coordination chemistry is an interdisciplinary science that makes a bridge between inorganic, organic, physical, analytical, and biological chemistry.