The mechanism of CO2 insertion into iridium(I) hydroxide and alkoxide bonds : a kinetic and computational study

The ERC (Advanced Researcher Award FUNCAT to SPN), the EPSRC and Sasol technology (Stipend to BJT) are gratefully acknowledged for support. Umicore AG are thanked for their generous gift of materials. SPN is a Royal Society Wolfson Award holder. PBW holds a Royal Society Industry Fellowship.The facile insertion of CO2 into iridium(I) hydroxide, alkoxide, and amide bonds was recently reported. In particular, [Ir(cod)(IiPr)(OH)] (IiPr=1,3-bis(isopropyl)imidazol-2-ylidene) reacted with CO2 in solution and in the solid state in a matter of minutes to give the novel [{Ir(cod)(IiPr)}2(μ-κ1O:κ2O,O-CO3)] complex. In the present study, this reaction is probed using kinetics and theoretical studies, which enabled us to analyse its facile nature and to fully elucidate the reaction mechanism with excellent correlation between the two methodsPostprintPeer reviewe