The ligand polyhedral model approach to the mechanism of complete carbonyl exchange in [Rh4(CO)12] and [Rh6(CO)16].

The Ligand Polyhedral Model (LPM) is applied to the carbonyl scrambling observed on the NMR timescale for the two cluster carbonyls [Rh-4(CO)(12)] and [Rh-6(CO)(16)]. For [Rh-4(CO)(12)] the NMR data is completely consistent with the libration of the Rh-4 central core about a C-3 - rotational axis within the icosahedral shell of twelve CO ligands leading to a single-step concerted exchange process. Rotation of the Rh-4 unit is also found to lead to the formation of a new all terminally bonded isomer which retains the icosahedral shell of CO ligands. Importantly, this new isomer does not have the [Ir-4(CO)(12)] structure which is known to possess an cube-octahedral ligand shell. With [Rh-6(CO)(16)] and its substituted derivative [Rh-6(CO)(15)L] exchange is considered to take place via a polyhedral inter-conversion in which the external tetra-capped truncated tetrahedral shell of carbonyl ligands observed in the ground-state undergoes rearrangement first to the 2 : 6 : 6' : 2 complementary geometry and then returns to the ground-state structure. This leads to a single-step fully concerted CO exchange. The LPM approach also provides an understanding of the variation of activation energies observed in going from [Rh-4(CO)(12)] to [Rh-6(CO)(16)] and of the driving force to the fluxional process.