Anisotropic Metal-Metal Pauli Repulsion in Polynuclear d 10 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 (Wan, Q., Proc. Natl. Acad. Sci. U. S. A. 2021, 118, e2019265118). 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- n d 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.