Dissecting the Bond Formation Process of $d^{10}$-Metal-Ethene Complexes with Multireference Approaches

TL;DR

This study uses advanced multireference computational methods to analyze how ethene bonds to nickel and palladium centers, revealing differences in bonding strength and covalency influenced by ligand orientation.

Contribution

It applies a combination of multireference and density functional approaches to dissect the bonding mechanisms in metal-ethene complexes, providing new insights into their electronic structure.

Findings

Perpendicular ethene ligands stabilize the complex via double-back-bonding.

Nickel-ethene complexes exhibit stronger covalent interactions than palladium counterparts.

Bonding analysis varies with ligand orientation and metal type.

Abstract

The bonding mechanism of ethene to a nickel or palladium center is studied by the density matrix renormalization group algorithm, the complete active space self consistent field method, coupled cluster theory, and density functional theory. Specifically, we focus on the interaction between the metal atom and bis-ethene ligands in perpendicular and parallel orientations. The bonding situation in these structural isomers is further scrutinized using energy decomposition analysis and quantum information theory. Our study highlights the fact that when two ethene ligands are oriented perpendicular to each other, the complex is stabilized by the metal-to-ligand double-back-bonding mechanism. Moreover, we demonstrate that nickel-ethene complexes feature a stronger and more covalent interaction between the ligands and the metal center than palladium-ethene compounds with similar coordination spheres.