Functionalization of 3-Iridacyclopentenes

Members of a series of iridacyclopentenes of composition [TpMe2Ir(k2-C,C-CH2CR′=CRCH2)(CO)] (TpMe2=hydrotris(3,5-dimethylpyrazolyl)borate; R=R′=H, 1; R=Me, R′=H, 2; R=R′=Me, 3) have been subjected to common organic chemistry procedures for hydrogenation, cyclopropanation, epoxidation, water addition through hydroboration, cis-dihydroxylation, and ozonolysis. The stability of metallacycles 1–3, imparted by the presence of the co-ligands TpMe2 and CO, directs the reactivity towards the C=C double bonds, and furthermore the stereochemistry of the products formed is strongly dictated by the steric demands of the TpMe2 ligand. While the products obtained in some of the above-mentioned reactions are the expected ones from an organic chemistry point of view, in other cases the results differ from the outcomes of similar reactions carried out with the all-carbon counterparts.