LAUSR

The free energy for hydride transfer reactions of transition metal hydrides is known to be influenced by solvent effects. The first-row transition metal hydride [HNi(dmpe)2][BF4] (dmpe = 1,2-bis(dimethylphosphino)ethane) has starkly different hydride transfer reactivities with CO2 in different solvents. A binary mixture of water and acetonitrile was used to tune the hydride transfer reactivity of HNi(dmpe)2+ with CO2 so that the free energy for this reaction approached zero. Various mole fractions of water were tested and a linear relationship between the hydride transfer free energy and solvent composition was established for 0-0.24 mole fraction of water. A deviation from linearity was found upon moving toward higher mole fractions of water. The tuning of the free energy for hydride transfer allowed HNi(dmpe)2+ to be used as a catalyst for the hydrogenation of CO2. The optimized catalyst conditions produced 58 turnovers at room temperature in 0.082 mole fraction of water using 60 atm of a 1:1 mixture of H2 to CO2 gas.