Metal-metal bonds in bimetallic complexes have attracted attention due to their unique electronic structures and range of applications in catalysis. Here we report the synthesis, characterization and systematic investigation into the electronic structures of a series of homo-bimetallic iron, cobalt and nickel complexes supported by bis(4-tert-butyl-2,6-pyridinediimine) macrocyclic ligands (3PDI2). These complexes span five consecutive cluster electron counts, allowing for the development of a model that explains our observation of metal-metal bond weakening concomitant with ligand reduction. This phenomenon appears to arise from population of a molecular orbital containing both metal-metal σ* character and ligand π* character, as suggested by computational studies. These data indicate that the strength of metal-metal bonds can be tuned through the use of redox-active ligands, which provide orbitals that are close in energy to the d-manifold but exhibit poor spatial overlap with the metal-based orbitals.

Investigation into metal-metal bonding interactions and ligand redox-activity in a series of homobimetallic complexes

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.