We analyzed the electronic and structural properties of an α-Keggin type molybdenumbased polyoxometalate (POM) [[PMo 12 O 40 ] 3− ] and its capacity for reduction reaction via H adsorption using ab initio calculations based on density functional theory (DFT). We also determined the change in the electronic properties brought about by vanadium substitutional doping, and its effect on the capacity of POM to adsorb H atom. We found that the optimal substitutional doping of four vanadium per one unit of POM is adequate to maintain its structural stability. Furthermore, increasing dopant concentration changes charge redistribution such that it induces charge transfer to an initially less active sites for H adsorption on pristine POM. This may increase the possibility of creating active sites from an initially inert H adsorption sites and allows for a higher density of H adsorption. This phenomenon could be relevant for chemical reactions that initially requires high number of pre-adsorbed H atoms.

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Dicationic thiolate-bridged diruthenium complexes bearing sterically bulky alkane substituents on the thiolate ligands such as [Cp*Ru­(μ-S i Pr)2Ru­(OH2)­Cp*]­(OTf)2 have been found to work as effective catalysts toward oxidation of molecular dihydrogen into protons and electrons in protic solvents such as water and methanol. DFT calculations indicate that the sterically bulky alkane substituent in the complex plays an important role in facilitating the reaction step of the coordination of molecular dihydrogen.