Investigating the structure, bonding, and energy decomposition analysis of group 10 transition metal carbonyls with substituted terminal germanium chalcogenides [ M (CO) 3 Ge X ] ( M = Ni, Pd, and Pt; X = O, S, Se, and Te) complexes: insight from first-principles calculations

Context This research focused on the theoretical investigation of transition metal carbonyls [ M (CO) 4 ] coordinated with terminal germanium chalcogenides complexes [ M (CO) 3 Ge X ], where M represents Ni, Pd, and Pt and X represents O, S, Se, and Te labeled 1 – 15 . While the notable complexes M (CO) 4 (where M = Ni, Pd, Pt) numbered 1 , 6 , and 11 are of significance, substituting one of the CO ligands in 1, 6, and 11 with a Ge X ligand (where X = O, S, Se, or Te) result in substituted complexes (2–5 , 7–10 , and 11–15 ). Substituting of the CO ligand slightly alters these bond angles. Specifically, the ∠CMC bond angles for [Ni] complexes range from 111.9° to 112.2°, for [Pd] complexes from 111.4° to 111.7°, and for [Pt] complexes from 112.4° to 112.8°. These findings indicate a minor deviation from the tetrahedral geometry due to the influence of the new GeX ligand. Similarly, there is a slight change in the geometry of the metal complexes, where the ∠GeMC angles for [Ni] complexes are between 106.7° and 106.9°, for [Pd] complexes between 107.2° and 107.5°, and for [Pt] complexes between 105.9° and 106.4°. Comparing among the substituted GeX complexes, those containing GeTe exhibit a higher natural bond orbital (NBO) contribution from the Ge atom compared to the M atom. Consequently, based on the above observations, it can be inferred that Ge X acts as an effective sigma donor in contrast to carbonyl compounds. Results of energy decomposition analysis (EDA) for the M –CO bond in 1 , 6 , and 11 and for the M –Ge X bond in the other [ M (CO) 3 (Ge X )] complexes where M = Ni, Pd and Pt. The percentage contribution of Δ E elstat and Δ E orb shows a relatively identical behavior for all ligands in case of each metal complexes. Methods Density functional theory (DFT) calculations were conducted using the B3LYP/gen/6-31G*/LanL2DZ level of theory to examine transition metal carbonyls [ M (CO) 4 ] coordinated with terminal germanium chalcogenides complexes [ M (CO) 3 Ge X ], where M represents Ni, Pd, and Pt, and X represents O, S, Se, and Te labeled 1–15 utilized through the use of Gaussian 09W and GaussView 6.0.16 software packages. Post-processing computational code such as multi-wave function was employed for results analysis and visualization.