Thermodynamic Hydricity of Transition Metal Hydrides
2016/08/02 by Eric S. Wiedner, Matthew B. Chambers, Catherine L. Pitman +3 · 553 citations
Chemical Engineering · Chemistry · #Acetonitrile #Ammonia Synthesis and Nitrogen Reduction #Asymmetric Hydrogenation and Catalysis #Bond cleavage #Carbon dioxide utilization in catalysis #Catalysis #Chemistry #Computational chemistry #Heterolysis #Hydride #Inorganic chemistry #Metal #Organic chemistry #Photochemistry #Physical chemistry #Reactivity (psychology) #Stoichiometry #Transition metal
paper · doi:10.1021/acs.chemrev.6b00168
published in Chemical Reviews 116(15), 8655-8692 (American Chemical Society)
openalex publication_date 2016/08/02 · openalex created_date 2016/08/23 · openalex updated_date 2026/07/30
Abstract
Transition metal hydrides play a critical role in stoichiometric and catalytic transformations. Knowledge of free energies for cleaving metal hydride bonds enables the prediction of chemical reactivity, such as for the bond-forming and bond-breaking events that occur in a catalytic reaction. Thermodynamic hydricity is the free energy required to cleave an M-H bond to generate a hydride ion (H(-)). Three primary methods have been developed for hydricity determination: the hydride transfer method establishes hydride transfer equilibrium with a hydride donor/acceptor pair of known hydricity, the H2 heterolysis method involves measuring the equilibrium of heterolytic cleavage of H2 in the presence of a base, and the potential-pKa method considers stepwise transfer of a proton and two electrons to give a net hydride transfer. Using these methods, over 100 thermodynamic hydricity values for transition metal hydrides have been determined in acetonitrile or water. In acetonitrile, the hydricity of metal hydrides spans a range of more than 50 kcal/mol. Methods for using hydricity values to predict chemical reactivity are also discussed, including organic transformations, the reduction of CO2, and the production and oxidation of hydrogen.
Citations
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