Ammonia Synthesis through Hydrolysis of a Trianionic Pincer Ligand-Supported Molybdenum-Nitride Complex

Reported is the hydrolysis of a homogeneous Mo-nitride complex bearing a trianionic pincer-type ligand to produce ammonia. Treating the anionic [(ONO)]Mo equivalent to N(OtBu)]Ph3PCH3 with two equivalents of water produces ammonia and the dioxo complex [(ONO)]MoO2]Ph3PCH3. X-Ray crystal structures of the starting nitrido complex and product dioxo complex are presented. Evidence for ammonia release comes from GC-MS and deuterium-labelling studies. The reaction is presented in the context of a two-stage solar thermochemical dinitrogen fixation process as the solid-state nitride hydrolysis step.