Identifying novel ligand types in organometallic chemistry requires a grasp of isoelectronic or isolobal interactions. A clear way to apply the isolobal relationship is in structural interpretation. Structures that appear isolobal can be fundamentally understood through this analogy. In 1981, Hoffmann introduced, ‘‘Two fragments are isolobal if the number, symmetry properties, approximate energy and shape of the frontier orbitals and the number of electrons in them are similar but not identical.’’ BF, SiO, N2, and GaI are examples of well-known ligands with similar isoelectronic characteristics to carbon monoxide [1]. Small molecule activation, particularly that of N2, using various metal complexes and further functionalization, is still a challenge [[2], [3], [4], [5]]. Metal carbonyl complexes have recently gained considerable attention in both theoretical and experimental studies due to their flexibility in catalytic applications, serving as either spectator ligands or active reactants. Experimentally, different types of transition metal (Mn, Ru, Co, Mo) carbonyl complexes have been synthesized and used for different applications such as anticancer studies, catalysis, and as CO-releasing molecules [6,7]. In the synthesis of organic molecules, as catalysts or precursors for homogeneous catalysis, and in biomedical applications, metal carbonyls play a critical role [[8], [9], [10], [11], [12], [13], [14], [15]]. It has been used in various industrial processes, including polymer synthesis, carbonylation, Wittig reaction, as photo redox catalysts for organic synthesis, and olefin synthesis [[16], [17], [18], [19], [20], [21]]. Coordination chemistry, particularly the study of transition metal cluster compounds, is experiencing rapid growth and drawing increasing interest from research communities worldwide [[22], [23], [24], [25]]. The compound featuring the isoelectronic species SiO with silver was initially identified by Schnöckel et al., in 1988. The Ag(SiO) complex is formed when silver metal and SiO molecules co-condense in the presence of a substantial amount of argon. Infrared spectroscopy was employed to confirm the formation of the Ag(SiO) complex [26]. Alikhani has extensively investigated the bonding interactions between SiO molecules and various metals. His initial studies focused on the bonding of atomic silver with SiO and SiS, revealing a pronounced covalent character [27]. Additionally, Weltner Jr. And colleagues examined the ESR patterns of mono carbonyls at 4 K in a solid neon matrix, using transition-metal monosilonyls and their associated carbonyl complexes [28]. Research on different kinds of metal silyl carbonyls is what people are looking for. An essential part of organometallic chemistry is played by iron carbonyl compounds. Iron carbonyls are fundamental to organometallic chemistry, with Fe(CO)5, Fe2(CO)9, and Fe3(CO)12 being among the most commonly studied examples. Among these, Fe(CO)5, the mononuclear species, has received the most extensive attention in both theoretical and experimental research [[29], [30], [31]]. Hoffmann et al. examined how the bonding patterns of [Fe(SiO)5] and [Fe(CO)4(SiO)] differed from those of other isoelectronic complexes with ligands such as carbonyl, dinitrogen, and boron fluoride. It is well known that CO is a good donor and acceptor [32]. Binuclear ethylenedithiolate iron carbonyls were recently the subject of structural analysis by King et al. The hexacarbonyl H2C2S2Fe2(CO)6 were decarbonylated, giving rise to the lowest energy singlet pentacarbonyl H2C2S2Fe2(CO)5 [33]. To explore potential substitutes for carbonyl ligands in organometallic frameworks, Jeyakumar and colleagues conducted a theoretical study on 32 unique Fe(CO)4 (A–X) complexes, where group 13 monohalides were introduced as ligands (A = B, Al, Ga, or In; X = F, Cl, Br, or I) [[34], [35], [36], [37], [38]]. Building on this, the same research group carried out DFT-based structural and bonding analyses on Ni, Pd, and Pt carbonyl complexes coordinated with terminal halo Y ligands [TM(CO)3YX], where Y = B, Al, Ga, or In and X = F, Cl, Br, or I. Their investigations have also encompassed a broader range of transition metal carbonyl complexes [[39], [40], [41], [42], [43]]. Only a limited number of studies have reported the coordination of lead-based compounds to metal centres [[44], [45], [46]]. In the present work, we focus on the structural and bonding properties of [Fe(CO)4(PbX)] complexes (X = O, S, Se, and Te), comparing them with the parent compound Fe(CO)5. A total of eight [Fe(CO)4(PbX)] isomers, featuring Pb–X ligands in both axial and equatorial positions, were examined using NPA, NBO, EDA, CDA, and WBI techniques. This study offers new insights into the isolobal and isoelectronic replacement of CO ligands by Pb–X groups in Fe(CO)5, enhancing our understanding of PbX (X = O, S, Se, Te) as alternative ligands in comparison with CO and N2.