Bio-mimetic self-assembled computationally designed catalysts of Mo and W for hydrogenation of CO/dehydrogenation of HCOOH inspired by the active site of formate dehydrogenase

Density functional theory modelling has been used to design Mo and W-based catalysts MoIII( t Bu)(CO) and WIII( t Bu)(CO) for CO 2 hydrogenation and HCOOH dehydrogenation, which are bio-mimics of the active site of formate dehydrogenase. Based on DFT calculations, the molybdenum and tungsten based complexes are good catalysts in the +3 oxidation state for CO 2 hydrogenation with free energies of 24.03 and 21.31 kcal mol −1 , respectively. Such a low barrier indicates that our newly designed Mo and W-based complexes are very efficient for CO 2 hydrogenation or HCOOH dehydrogenation catalysis. Overall, our computational results provide in depth insights that can serve as a great tool for the design and development of new and efficient molybdenum and tungsten based catalysts for CO 2 hydrogenation or HCOOH dehydrogenation. Bio-inspired Mo and W based catalysts have been designed for catalytic conversion of CO 2 to HCOOH or vice versa by stepwise assessment of the chemical environment around the metal center using state-of-the-art density functional theory.