RESUMO
A series of Cp*Ir (Cp* = pentamethylcyclopentadienyl) complexes with amidated 8-aminoquinoline ligands were synthesized and tested for formic acid (FA) dehydrogenation. These complexes showed improved activities compared to pristine 8-anminquinoline (L1). Specially, amidation changed the outer coordination sphere of the complex (3) bearing N-8-quinolinylformamide (L3), and 3 was proved to be a proton-responsive catalyst. Our experimental results and DFT calculations demonstrated that the deprotonated carbanion in L3 could interact with a water molecule to stabilize the transition states and lower the reaction energy barrier, which improved the reaction activity. A turnover frequency of 206250 h-1 was achieved by 3 under optimized conditions. This study presents a method to develop new ligands and modify the existing ligands for efficient FA dehydrogenation.
RESUMO
Hydrogen can be used as an energy carrier for renewable energy to overcome the deficiency of its intrinsically intermittent supply. One of the most promising application of hydrogen energy is on-board hydrogen fuel cells. However, the lack of a safe, efficient, convenient, and low-cost storage and transportation method for hydrogen limits their application. The feasibility of mainstream hydrogen storage techniques for application in vehicles is briefly discussed in this Review. Formic acid (FA), which can reversibly be converted into hydrogen and carbon dioxide through catalysis, has significant potential for practical application. Historic developments and recent examples of homogeneous noble metal catalysts for FA dehydrogenation are covered, and the catalysts are classified based on their ligand types. The Review primarily focuses on the structure-function relationship between the ligands and their reactivity and aims to provide suggestions for designing new and efficient catalysts for H2 generation from FA.