Activation of aldehydes by exocyclic iridium(i)-η⁴:π²-diene complexes derived from 1,3-oxazolidin-2-ones

The Ir(i) complexes [Tp^Me2Ir(η⁴-1,4-diene)] 2b and 2c react thermally with a variety of aromatic aldehydes, 3a-e, to generate the metallabicyclic compounds 4e-k and the Fischer-type carbenes 5a-b in moderate yields. These reactions are proposed to take place with the initial formation of η¹-aldehyde adducts as key intermediates. The formation of the metallabicyclic compounds 4e-k involves a formal decarboxylation process at the exo-2-oxazolidinone diene and an ortho metallation of the aromatic ring. The generation of the Fischer-type carbenes 5a-b is the result of a series of metal-based rearranged intermediates with no decarboxylation observed. Treatment of the η⁴-diene complex 2b with a variety of Lewis bases induces a change in the binding mode of the diene ligand from η⁴:π² to η²:σ² to form the Ir(iii) derivatives 6b-d of composition Tp^Me2Ir-(η⁴:π²-1,4-diene)(L) (L = CO, MeCN, and C₅H₅N). A study of reactions of complex 2b with either mono- or poly-deuterated aldehydes was performed to understand the mechanisms of such processes. The results of these studies were used to determine plausible formation mechanisms of the metallabicyclic compounds 4e-4k and Fischer-type carbenes 5a-b compound series. These mechanisms were corroborated by density functional theory (DFT) calculations of the free energy profiles.