Metal-metal singly bonded [Rh2(CO)4(acac)2][OTf]2 (1) has been synthesized and characterized by spectroscopic and analytical techniques. A density functional theory (DFT) optimized structure has been computed for the unbridged centro-symmetric structure. Reaction of 1 with PIN.HBr results in the [Rh(PIN)2(H2O)Br][OTf]2 (2) in high yield. The reaction involves metal-oxidation from RhII to RhIII accompanied by the metal-metal bond cleavage. The X-ray structure of 2 has been determined which reveals the incorporation of two N-heterocyclic carbene (NHC) ligands to each rhodium. This work demonstrates the general utility of the metal-metal bonded compounds for the easy synthesis of metal-NHC compounds.