The development of well-understood, easily tuneable ligands has become important in the discovery and synthesis of new catalysts and catalytic systems. PCP pincer ligands, due to their tunability and stability, have been used in a variety of catalytic systems since their discovery over 30 years ago. In this work, two bis-(2-(dialkylphosphino)phenyl)methane ligands were complexed with rhodium through single and double C-H activations to give PC(sp3)P and PC(carbene)P complexes. The mechanism of ligand attachment through C-H activation was explored through the isolation and characterization of intermediates. The structure of the subsequently formed complexes, as well as their reactivity with small molecules such as H2, CO, O and N2O was also explored.