The novel tridentate ligand cis,cis-1,3,5-tris[(diphenylphosphino)methyl]cyclohexane (6) has been synthesized and treated with [Rh(COD)Cl]2. Intramolecular metalation of a CH bond of the cyclohexane ring occurs (7). Studies with D2 gas and 6[D6] prove that axial and equatorial CH bonds are metalated and that a mutual exchange occurs in this process. Replacement of the Cl− by the SbF−6 anion in 7 results in a reduced interaction between the metal and the CH bond (8). 7 reacts with CO to form the carbonyl 9 where no such interaction is observed.