Redox-Dependent Metal-Metal Bonding in Trinuclear Metal Chains: Probing the Transition from Covalent Bonding to Exchange Coupling

The synthesis and physical properties of two new cationic tri-metallic chains, [(PEt3)(3)RuCl3MCl3Ru(PEt3)(3)](1+), M=Rh and Ir are reported. These are isostructural with a previously reported 17-electron all-ruthenium analogue, but replacing a d(5) Ru-III ion in the central position with d(6) Rh-III/Ir-III has a significant impact on the nature of the metal-metal interactions. All three materials have been characterized electrochemically at the 18-, 17- and 16-electron levels. X-ray crystallography and spectroelectrochemistry, complemented by electronic structure analysis at the DFT and CASPT2 levels, indicate that whilst the presence of a Ru-III ion in the center of the chain allows multi-center covalent bonding to develop, a closed-shell Rh-III/Ir-III ion pushes the system towards the exchange-coupled limit, where the outer Ru centers are only weakly interacting. This family of three isostructural compounds reveals how changes in metal composition can have subtle effects on physical properties of systems that lie close to the localized/delocalized borderline.