Unprecedented combination of regioselective hydrodefluorination and ligand exchange reaction during the syntheses of tris-cyclometalated iridium(iii) complexesElectronic supplementary information (ESI) available. CCDC 876293. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt32071a

The first reported combination of regioselective hydro-defluorination and a ligand exchange reaction during the syntheses of neutral iridium( iii ) complexes is presented. Surprisingly, loss of one fluorine atom per ligand combined with a complete ligand exchange reaction on the transition metal were jointly observed during a bridge-splitting and substitution reaction of two different dimeric iridium( iii ) precursor complexes with two different ancillary ligands. The regioselectivity of defluorination was evidenced in both cases. The reaction time was identified as a factor strongly impacting the kinetics of the thermally induced reaction. The first reported combination of regioselective hydro-defluorination and a ligand exchange reaction during the syntheses of neutral iridium( iii ) complexes is presented.