Experimental and theoretical study of intramolecular exchange in Ir2Rh2(CO)12 and Ir4(CO)11(µ-SO2)

Abstract

As observed by variable-temperature and -pressure ¹³C NMR, intramolecular carbonyl scrambling in Ir₂Rh₂(CO)₁₂ and Ir₄(CO)₁₁(µ-SO₂) proceeds via a ‘change of basal face’ mechanism. In both cases the site exchange process has a positive activation volume suggesting that the transition states contain longer M–M distances compared to ground states of C_s symmetry. Transition state structures have been located by density functional calculations including relativistic effects. These structures contain a new symmetry plane which interchanges the indistinguishable starting and final geometries. Both transition state structures contain one significantly elongated M–M distance, bearing the bridging ligand unaffected by the site exchange. Differences in molecular volumes of ground and transition state geometries as calculated from Connolly surfaces and electron densities confirm the volume expansion in both cases. The sign of the activation volume is therefore a good criterion for distinguishing between the two main site exchange processes occurring in tetrahedral d⁹ carbonyl clusters, i.e. the ‘change of basal face’ process and the ‘merry-go-round’ process, as the latter presents a negative activation volume.