A density functional study of intra- and interring haptotropic η2,η2 rearrangements in rhodium, ruthenium, and osmium naphthalene complexes

Abstract

The density functional theory method was used to perform quantum-chemical modeling of the mechanisms of η2,η2-intraring (Intra-HR) and η2,η2-interring (Inter-HR) haptotropic rearrangements for μ2 complexes of naphthalene with rhodium, ruthenium, and osmium. The structure of transition states and intermediates was studied, and the energy parameters of haptotropic rearrangements in these complexes were determined. We used the PBE functional, the TZV2p three-exponential basis set for valence electrons, and the SBK-JC relativistic pseudopotential for core electrons. η2,η2 Intra-HR was found to occur inside the aromatic ring of η2 naphthalene complexes without going outside it through intermediates and transition states with ηn structures (n = 1, 2). Inter-HR occurred as metal replacements on the periphery of the naphthalene ligand through intermediates and transition states with ηn structures (n = 1, 2, 3) from one ring into another. The calculated activation barriers for η2,μ2 Intra-HR and η2,η2 Inter-HR in the complexes studied closely agree with their experimental values.