4.8 Article

Cleavage and Formation of Molecular Dinitrogen in a Single System Assisted by Molybdenum Complexes Bearing Ferrocenyldiphosphine

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 53, Issue 43, Pages 11488-11492

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201405673

Keywords

dinitrogen complexes; Haber-Bosch process; iron; molybdenum; nitrogen fixation

Funding

  1. Japan Society for the Promotion of Science (JSPS) [24109014]
  2. Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT)
  3. MEXT
  4. Grants-in-Aid for Scientific Research [26288044, 26888008, 26620075, 26410110, 26105708, 24109014] Funding Source: KAKEN

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The NN bond of molecular dinitrogen bridging two molybdenum atoms in the pentamethylcyclopentadienyl molybdenum complexes that bear ferrocenyldiphosphine as an auxiliary ligand is homolytically cleaved under visible light irradiation at room temperature to afford two molar molybdenum nitride complexes. Conversely, the bridging molecular dinitrogen is reformed by the oxidation of the molybdenum nitride complex at room temperature. This result provides a successful example of the cleavage and formation of molecular dinitrogen induced by a pair of two different external stimuli using a single system assisted by molybdenum complexes bearing ferrocenyldiphosphine under ambient conditions.

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