Monomeric Chini-Type Triplatinum Clusters Featuring Dianionic and Radical-Anionic pi*-Systems

摘要

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(m-CO)(3)(CNArDipp2)(3)](n-) (n= 0, 1, 2), which represents a unique set of monomeric Pt-3 clusters supported by pi-acidic ligands. Spectroscopic, computational, and synthetic investigations demonstrate that the highest-occupied molecular orbitals of the mono-and dianionic clusters consist of a combined pi*-framework of the CO and CNArDipp2 ligands, with negligible Pt character. Accordingly, this study provides precedent for an ensemble of carbonyl and isocyanide ligands to function in a redox noninnocent manner.