Our aim was to develop the synthetic potential and reaction chemistry of Ir3+ and Ru2+ electrophiles by preparing well-characterized complexes whose properties are controllable by modification of the ancillary ligand environment Specifically, we prepared a series of ruthenium complexes to serve as selective hydrogenation and hydrogenolysis catalysts of furan derivatives. We also expanded the synthesis of electrophilic Ir3+ di-thiolate complexes. These types of compounds could eventually serve as catalysts precursors for the addition of weak nucleophiles to alkynes and nitriles.