Designing Catalytic Systems Using Binary Solvent Mixtures: Impact of Mole Fraction of Water on Hydride Transfer.

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)][BF] (dmpe = 1,2-bis(dimethylphosphino)ethane) has starkly different hydride transfer reactivities with CO in different solvents. A binary mixture of water and acetonitrile was used to tune the hydride transfer reactivity of HNi(dmpe) with CO so that the free energy for this reaction approached zero.