Drastic Tuning of the Electronic Structures of Diruthenium Aryl Complexes by Isoelectronic Axial Ligands

Reported herein is the use of aryls as axial ligands to manipulate reactivity at the distal metal site through metal-metal-ligand interactions in diruthenium paddlewheel complexes. The vacant ruthenium site in Ru₂(ap)₄(Ar) (1; ap = 2-anilinopyridinate and Ar = C₆H₄-4-NMe₂), thus rendered reactive, is able to bind a series of isoelectronic ligands to afford three complexes of the form (Y)[Ru₂(ap)₄](Ar) [Y = CN^- (2), HC≡C^- (3), CO (4)], each of which exhibits a distinct electronic structure. While reactions with anionic ligands subsequently result in oxidation of the diruthenium core from Ru₂(II,III) to Ru₂(III,III), the reaction with CO yields a rare example of a Ru₂(II,III)-CO_axial adduct. The latter reaction is particularly interesting in its completely reversible change of the ground state from S = ³/₂ in 1 to S = ¹/₂ in 4, the first of its kind seen in Ru₂(II,III) species. In general, this work sheds light on the modulation of the electronic structure of diruthenium paddlewheel complexes using distinct coordination environments around each of the ruthenium centers.