Monomeric Chini‐Type Triplatinum Clusters Featuring Dianionic and Radical‐Anionic π*‐Systems

Owing to their unique topologies and abilities to self‐assemble into a variety of extended and aggregated structures, the binary platinum carbonyl clusters [Pt 3 (CO) 6 ] n 2− (“Chini clusters”) continue to draw significant interest. Herein, we report the isolation and structural characterization of the trinuclear electron‐transfer series [Pt 3 (μ‐CO) 3 (CNAr Dipp2 ) 3 ] n − ( n =0, 1, 2), which represents a unique set of monomeric Pt 3 clusters supported by π‐acidic ligands. Spectroscopic, computational, and synthetic investigations demonstrate that the highest‐occupied molecular orbitals of the mono‐ and dianionic clusters consist of a combined π*‐framework of the CO and CNAr Dipp2 ligands, with negligible Pt character. Accordingly, this study provides precedent for an ensemble of carbonyl and isocyanide ligands to function in a redox non‐innocent manner.