Reversible hydrogen adsorption at room temperature using a molybdenum-dihydrogen complex in the solid state

Reversible H₂storage under mild conditions is one of the most important targets in the field of materials chemistry. Dihydrogen complexes are attractive materials for this target because they possess moderate adsorption enthalpy as well as adsorption without cleavage of the H-H bond. In spite of these advantages, H₂adsorption studies of dihydrogen complexes in the solid state are scarce. We herein present H₂adsorption properties of the 16-electron precursor complex ([Mo(PCy₃)₂(CO)₃]) in the solid state synthesized by two procedures. One is the direct synthesis under an Ar atmosphere (1), and the other is removal of the N₂-adduct under vacuum (2).2showed ideal Langmuir type reversible ad/desorption of H₂above room temperature, whereas1showed irreversible adsorption. The adsorption enthalpy of2was larger than that in THF solution. Using DFT calculation, this difference was explained by the absence of the agostic interaction in the solid state.