Solution multinuclear and multidimensional NMR analyses of the [(triphos)Rh(η1:η2-P4RR′)]n+ complex cations [triphos = MeC(CH2PPh2)3; R = H, Me, Ph; R′ = lone pair, H, Me; n = 0, 1] confirm the same primary structure determined by X-rays in the solid state. In addition, 2D 1H NOESY and 31P{1H} exchange NMR spectroscopy show that these complexes are nonrigid on the NMR time-scale over the 253–318 K temperature range. A dynamic process that involves the terminal phosphane groups of the triphos ligand is displayed by each compound. The NMR spectroscopic data indicate a slow scrambling motion in which the P4R unit tumbles with respect to the (triphos)Rh moiety. DFT calculations outline a possible turnstile mechanism involving the threefold and twofold rotors into which the complex is subdivided. The process goes through a transition state in which the axial and equatorial dispositions of the PRR′ and P=P donating groups of the P4RR′ ligand are inverted with respect to the ground state. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)