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≡N(OtBu)]Ph3PCH3 with two equivalents of water produces ammonia and the dioxo complex [(ONO)]MoO2]Ph3PCH3. X‐Ray crystal structures of the starting...

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Bibliographic Details
Published in:Chemistry : a European journal 2019-11, Vol.25 (62), p.14059-14063
Main Authors: Chakraborty, Jhonti, Mandal, Ushnish, Ghiviriga, Ion, Abboud, Khalil A., Veige, Adam S.
Format: Article
Language:English
Subjects:
Ammonia
ammonia synthesis
Chemistry
Coordination compounds
Crystal structure
Deuterium
homogeneous phase
Hydrolysis
Labeling
Ligands
Molybdenum
molybdenum nitride
Molybdenum oxides
nitride hydrolysis
Nitrides
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Summary:Reported is the hydrolysis of a homogeneous Mo‐nitride complex bearing a trianionic pincer‐type ligand to produce ammonia. Treating the anionic [(ONO)]Mo≡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. A first step towards solar‐powered ammonia synthesis: Modelling a heterogeneous two‐step solar thermochemical ammonia synthesis, hydrolysis of the trianionic pincer‐type molybdenum–nitrido complex [(ONO)Mo≡N]PPh3CH3 produces ammonia and the dioxo complex [(ONO)MoO2]PPh3CH3.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201903740