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

The Ir(I) complexes [TpMe2Ir(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 TpMe2Ir-(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.