Anisotropic Metal–Metal Pauli Repulsion in Polynuclear d<sup>10</sup> Metal Clusters
Shuo Xu, Qingyun Wan, Jun Yang, Chi‐Ming Che
Abstract
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.