Boosting Effect of Sterically Protected Glucosyl Substituents in Formic Acid Dehydrogenation by Iridium(III) 2‐Pyridineamidate Catalysts
Caterina Trotta, Vincenzo Langellotti, Immacolata Manco, Gabriel Menendez Rodriguez, Luca Rocchigiani, Cristiano Zuccaccia, Francesco Ruffo, Alceo Macchioni
Abstract
Abstract [Cp*Ir(R‐pica)Cl] (Cp*=pentamethylcyclopentadienyl anion, pica=2‐picolineamidate) complexes bearing carbohydrate substituents on the amide nitrogen atom (R=methyl‐β‐D‐gluco‐pyranosid‐2‐yl, 1 ; methyl‐3,4,6‐tri‐ O ‐acetyl‐β‐D‐glucopyranosid‐2‐yl, 2 ) were tested as catalysts for formic acid dehydrogenation in water. TOF MAX values over 12000 h −1 and 50000 h −1 were achieved at 333 K for 1 and 2 , respectively, with TON values over 35000 for both catalysts. Comparison with the simpler cyclohexyl‐substituted analogue ( 3 ) indicated that glucosyl‐based complexes are much better performing under the same experimental conditions (TOF MAX =5144 h −1 , TON=5000 at pH 2.5 for 3 ) owing to a lower tendency to isomerize to the less active k 2 ‐N,O isomer upon protonation. The 5‐fold increase in TOF MAX observed for 2 with respect to 1 is reasonably due to an optimal steric protection by the acetyl substituent, which may prevent unproductive inner‐sphere reactivity. These results showcase a powerful strategy for the inhibition of the common deactivation pathways of [Cp*Ir(R‐pica)X] catalysts for FA dehydrogenation, paving the way for the development of better performing hydrogen storage systems.