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N−H Bond Formation at a Diiron Bridging Nitride
Author(s) -
Zhang Shaoguang,
Cui Peng,
Liu Tianchang,
Wang Qiuran,
Longo Thomas J.,
Thierer Laura M.,
Manor Brian C.,
Gau Michael R.,
Carroll Patrick J.,
Papaefthymiou Georgia C.,
Tomson Neil C.
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202006391
Subject(s) - chemistry , protonation , bridging (networking) , bridging ligand , nitride , amide , redox , electron transfer , ligand (biochemistry) , crystallography , ammonia production , ammonia , proton coupled electron transfer , photochemistry , stereochemistry , inorganic chemistry , organic chemistry , crystal structure , receptor , ion , computer network , biochemistry , layer (electronics) , computer science
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 μ ‐amide product. The structurally analogous μ ‐silyl‐ and μ ‐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 NH 3 in high yield through a reaction that engages the redox‐activity of the ligand during PCET.