Anisotropic Metal-Metal Pauli Repulsion in Polynuclear d10 Metal Clusters

Metallophilicity has been widely considered to be the driving force for self-assembly of closed-shell d(10) metal complexes, but this view has been challenged by recent studies showing that metallophilicity in linear d(10)-d(10) dimers is repulsive. This is due to strong metal-metal (M-M ') Pauli repulsion (). Here, we study M-M ' Pauli repulsion in d(10) metal clusters. Our results show that M-M ' Pauli repulsion in d(10) polynuclear clusters is 6-52% weaker than in similar linear d(10) complexes due to the anisotropic shape of (n+1)s-nd hybridized orbitals. The overall M-M ' interactions in closed-shell d(10) polynuclear metal clusters remain repulsive. The effects of coordination geometry, relativistic effects, and the ligand's electronegativity on M-M ' Pauli repulsion in polynuclear d(10) clusters have been explored. These findings provide valuable guidance for the design and development of ligands and coordination geometries that alleviate M-M ' Pauli repulsion in d(10) metal cluster systems.