Strong metal-metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d⁸ and d¹⁰ organometallic complexes.

ABSTRACT: Metallophilicity is defined as the interaction among closed-shell metal centers, the origin of which remains controversial, particularly for the roles of spd orbital hybridization (mixing of the spd atomic orbitals of the metal atom in the molecular orbitals of metal complex) and the relativistic effect. Our studies reveal that at close M-M' distances in the X-ray crystal structures of d⁸ and d¹⁰ organometallic complexes, M-M' closed-shell interactions are repulsive in nature due to strong M-M' Pauli repulsion. The relativistic effect facilitates (n + 1)s-nd and (n + 1)p-nd orbital hybridization of the metal atom, where (n + 1)s-nd hybridization induces strong M-M' Pauli repulsion and repulsive M-M' orbital interaction, and (n + 1)p-nd hybridization suppresses M-M' Pa

SUBMITTER: Wan Q 

PROVIDER: S-EPMC7817198 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature