Interconversion of Formic Acid and Carbon Dioxide by Proton-Responsive, Half-Sandwich Cp*IrIII Complexes: A Computational Mechanistic Investigation

Dihydrogen (H-2) has many desirable features as a fuel, but utilization of H-2 is limited due to storage and transportation problems. A promising solution to these issues is reversible storage of hydrogen in the form of liquid-phase chemicals such as formic acid (FA), which could be accomplished by the development of efficient and robust catalysts. Recently, proton-responsive, half-sandwich Cp*Ir-III (where Cp* = pentamethylcyclo-pentadienyl anion) complexes capable of reversible hydrogen storage via interconversion between H-2/CO2 and formic acid/formate in water have been reported. This interconversion is performed via CO2 hydrogenation and FA dehydrogenation reactions and modulated by the pH of the medium. We report the results of a computational investigation of the mechanistic aspects of reversible hydrogen storage via two of these catalysts: namely, [Cp*Ir(4DHBP)](2+) (4DHBP = 4,4'-dihydroxy-2,2'-bipyridine) and [Cp*Ir(6DHBP)](2+) (6DHBP = 6,6'-dihydroxy-2,2'-bipyridine). Distinct features of the catalytic cycles of [Cp*Ir-(4DHBP)](2+) and [Cp*Ir(6DHBP)](2+). for CO2 hydrogenation and FA dehydrogenation reactions are demonstrated using density functional theory (DFT) calculations employing a "speciation" approach and probing deuterium kinetic isotope effects (KIE). In addition to the mechanistic insights and principles for the design of improved next-generation catalysts, the validation of computational methods for the investigation of the hydrogenation and dehydrogenation reactions is addressed.