Energy Partitioning Analysis of the Bonding in Ethylene and Acetylene Complexes of Group 6, 8, and 11 Metals: (CO)₅TM−C₂H<i>_x</i>and Cl₄TM−C₂H<i>_x</i>(TM = Cr, Mo, W), (CO)₄TM−C₂H<i>_x</i>(TM = Fe, Ru, Os), and TM⁺−C₂H<i>_x</i>(TM = Cu, Ag, Au)^,^,

Abstract

Quantum chemical calculations at the DFT level have been carried out for the title compounds. The equilibrium geometries and bond dissociation energies are reported. The nature of the bonding between the metal and the π ligands ethylene and acetylene has been investigated by means of an energy partitioning analysis. The nature of the metal−ligand interactions is not very different from each other in the donor−acceptor complexes (CO)5TM−C2Hx (TM = Cr, Mo, W), (CO)4TM−C2Hx (TM = Fe, Ru, Os), and TM+−C2Hx (TM = Cu, Ag, Au). The metal−C2Hx bonds have a slightly more electrostatic than covalent character. The covalent bonding comes mainly from the metal ← ligand σ donation and the metal → ligand π∥ in-plane back-donation. The contributions from the out-of-plane π⊥ and δ orbitals are negligible. The main difference of the bonding interactions in the metallacyclic compounds Cl4TM−C2Hx (TM = Cr, Mo, W) is that they are clearly more covalent than electrostatic. The covalent interactions come also mainly from a1(σ) and b2(π∥) interactions. The a2(δ) orbital interactions are negligible but the interactions of the out-of-plane π orbitals in the acetylene complexes Cl4TM−C2H2 contribute ∼11% to the total orbital term.