Reactions of cis- and trans-1,3-bis(di-t-butylphosphinomethyl)cyclohexane (cis- and trans-PCyP), with rhodium and palladium chlorides afforded C s and C 1 symmetrical pincer complexes, RhHCl(cis-PCyP), RhHCl(trans-PCyP), [(COD)Rh(μ-Cl) 2 RhH(trans-PCyP)], PdCl(cis-PCyP), and PdCl(trans-PCyP), where the PCyP ligands are coordinated in a meridianal fashion through the two phosphorus atoms and the cyclometalated C-1 carbon of the cyclohexane ring. The rhodium complexes were structurally characterized by X-ray diffraction. Isomers of the RhHCl(PCyP) and PdCl(PCyP) complexes were studied by DFT calculations.