Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 59, Issue 35, Pages 15215-15219Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202006391
Keywords
bimetallic complexes; iron nitrides; N-H bond formation; proton-coupled electron transfer; redox-active ligands
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Funding
- University of Pennsylvania
- American Chemical Society Petroleum Research Fund [57346-DNI3]
- National Institutes of Health [R35GM128794]
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Despite their connection to ammonia synthesis, little is known about the ability of iron-bound, bridging nitrides to form N-H bonds. Herein we report a linear diiron bridging nitride complex supported by a redox-active macrocycle. The unique ability of the ligand scaffold to adapt to the geometric preference of the bridging species was found to facilitate the formation of N-H bonds via proton-coupled electron transfer to generate a mu-amide product. The structurally analogous mu-silyl- and mu-borylamide complexes were shown to form from the net insertion of the nitride into the E-H bonds (E=B, Si). Protonation of the parent bridging amide produced ammonia in high yield, and treatment of the nitride with PhSH was found to liberate NH3 in high yield through a reaction that engages the redox-activity of the ligand during PCET.
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