Impact of Green Cosolvents on the Catalytic Dehydrogenation of Formic Acid: The Case of Iridium Catalysts Bearing NHC-phosphane Ligands

[Image: see text] The catalysts [Ir(COD)(κ(3)-P,C,P′-PC(NHC)P)]BF(4) and [Ir(COD)(κ(2)-P,C-PC(NHC)O)]BF(4) proved to be active in the solventless dehydrogenation of formic acid. The impact of various cosolvents on the activity was evaluated, showing an outstanding improvement of the catalytic performance of [Ir(COD)(κ(2)-P,C-PC(NHC)O)]BF(4)] in “green” organic carbonates: namely, dimethyl carbonate (DMC) and propylene carbonate (PC). The TOF(1h) value for [Ir(COD)(κ(2)-P,C-PC(NHC)O)]BF(4) increases from 61 to 988 h(–1) upon changing from solventless conditions to a 1/1 (v/v) DMC/HCOOH mixture. However, in the case of [Ir(COD)(PC(NHC)P)]BF(4), only a marginal improvement from 156 to 172 h(–1) was observed under analogous conditions. Stoichiometric experiments allowed the identification of various key reaction intermediates, providing valuable information on their reactivity. Experimental data and DFT calculations point to the formation of dinuclear species as the catalyst deactivation pathway, which is prevented in the presence of DMC and PC.