Synthesis and reactivity at the Ir-(Me)Tpm platform: from (1)-N coordination to (3)-N-based organometallic chemistry

Reaction of [Ir(-Cl)(COE)(2)](2) (COE = cis-cyclooctene) with tris(3,5-dimethylpyrazol-1-yl)methane ((Me)Tpm) affords [IrCl((1)-N-(Me)Tpm)(COD)] (1) (COD = 1,5-cyclooctadiene). The formation of 1 implies the transfer dehydrogenation of a COE ligand to give COD and COA (cyclooctane). A mechanistic proposal based on DFT calculations that explains this iridium promoted process has been disclosed. Additionally, reactivity studies have allowed the preparation and characterization, including determination of the molecular structures of a number of iridium complexes with the (Me)Tpm ligand in (1), (2) or (3)-N coordination modes. Moreover, the first example of an Ir-cyclooctyl complex featuring hydride and carbonyl ligands, whose solid state structure has been determined by X-ray diffraction methods, is reported.