Ligand-Centered Triplet Diradical Supported by a Binuclear Palladium(II) Dipyrrindione

Inorg Chem. 2021 Aug 16;60(16):12457-12466. doi: 10.1021/acs.inorgchem.1c01691. Epub 2021 Aug 4.


Oligopyrroles form a versatile class of redox-active ligands and electron reservoirs. Although the stabilization of radicals within oligopyrrolic π systems is more common for macrocyclic ligands, bidentate dipyrrindiones are emerging as compact platforms for one-electron redox chemistry in transition-metal complexes. We report the synthesis of a bis(aqua) palladium(II) dipyrrindione complex and its deprotonation-driven dimerization to form a hydroxo-bridged binuclear complex in the presence of water or triethylamine. Electrochemical, spectroelectrochemical, and computational analyses of the binuclear complex indicate the accessibility of two quasi-reversible ligand-centered reduction processes. The product of a two-electron chemical reduction by cobaltocene was isolated and characterized. In the solid state, this cobaltocenium salt features a folded dianionic complex that maintains the hydroxo bridges between the divalent palladium centers. X-band and Q-band EPR spectroscopic experiments and DFT computational analysis allow assignment of the dianionic species as a diradical with spin density almost entirely located on the two dipyrrindione ligands. As established from the EPR temperature dependence, the associated exchange coupling is weak and antiferromagnetic (J ≈ -2.5 K), which results in a predominantly triplet state at the temperatures at which the measurements have been performed.