DFT study of structural and electronic properties of [Fe(CO)4(PbX)] complexes (X = O, S, Se and Te): Influence of terminal lead chalcogenide ligands on bonding and stability
EDA; Iron carbonyl complexes; Lead chalcogenide ligands; NBO; WBI
Density Functional Theory (DFT) calculations at the B3LYP level were performed to investigate the structural and electronic properties of axial and equatorial isomers of [Fe(CO)4(PbX)] complexes, where X = O, S, Se, and Te. Total energy evaluations indicate that equatorial isomers are generally more stable than their axial counterparts. Detailed bonding analysis was carried out using Natural Population Analysis (NPA) and Energy Decomposition Analysis (EDA), providing insight into the nature of the FePbX interactions. The FePbX bond strengths were further assessed through Wiberg Bond Index (WBI) calculations. Frontier Molecular Orbital (FMO) analysis revealed HOMOLUMO gaps ranging from 3.04 to 3.97 eV, all of which are narrower than the corresponding gap in Fe(CO)5, suggesting enhanced electronic reactivity due to PbX substitution. Natural Bond Orbital (NBO) analysis indicated a greater electron density contribution from the Pb atom to the FePb bond, whereas for FeC bonds, carbon atoms contributed more significantly than Pb. These results collectively highlight the influence of terminal lead chalcogenide ligands on both the geometric and electronic structure of iron carbonyl complexes. 2025 Elsevier Inc.
Immanuel, Selvaraj; Manivarman, S.; Sivan, Akhil K.; Thomas, Jisha Mary; Nandhakumar, Velankanni; Paularokiadoss, Francisxavier; Christopher Jeyakumar, Thayalaraj
Journal of Molecular Graphics and Modelling;Volume;143;Issue;;Article No.;109250;
Restricted Access; Hardcopy may be available in the library
https://doi.org/10.1016/j.jmgm.2025.109250 https://www.scopus.com/pages/publications/105024336276?origin=resultslist
Immanuel S., PG and Research Department of Chemistry, St. Joseph's College of Arts and Science (Autonomous), Tamil Nadu, Cuddalore, 607001, India, PG and Research Department of Chemistry, Government Arts College, C-Mutlur, Tamil Nadu, Chidambaram, 608102, India; Manivarman S., PG and Research Department of Chemistry, Government Arts College, C-Mutlur, Tamil Nadu, Chidambaram, 608102, India; Sivan A.K., Department of Chemistry, MES College Marampally, Aluva, Kerala, Ernakulam, 683 105, India; Thomas J.M., Department of Chemistry, CHRIST University, Karnataka, Bengaluru, 560029, India; Nandhakumar V., Department of Biomaterials (Prosthodontics), Saveetha Dental College and Hospitals, Tamil Nadu, Chennai, 600077, India; Paularokiadoss F., PG and Research Department of Chemistry, St. Joseph's College of Arts and Science (Autonomous), Tamil Nadu, Cuddalore, 607001, India; Christopher Jeyakumar T., PG and Research Department of Chemistry, The American College (Autonomous), Tamil Nadu, Madurai, 625002, India