Ru265, [Ru2(μ-N)(NH3)8Cl2]Cl3, is a potent nanomolar inhibitor of the mitochondrial calcium uniporter (MCU), the transporter that mediates Ca2+ uptake into the mitochondria. This compound and related MCU inhibitors are promising therapeutic agents and chemical biology tools for studying intracellular Ca2+ dynamics. Axial ligand modification of these Ru-based complexes provides a facile way to tune their properties and make prodrugs. In this study, the use of axial phosphonate and phosphinate ligands was explored within this compound class, yielding [Ru2(μ-N)(NH3)8(OPO(OH)Me)2](CF3SO3)3 (1) and [Ru2(μ-N)(NH3)8(OPOPh2)2](CF3SO3)3 (2). Both complexes were characterized by multinuclear NMR spectroscopy, revealing downfield shifts of the 31P...