In:
Angewandte Chemie International Edition, Wiley, Vol. 59, No. 35 ( 2020-08-24), p. 15215-15219
Kurzfassung:
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.
Materialart:
Online-Ressource
ISSN:
1433-7851
,
1521-3773
DOI:
10.1002/anie.202006391
Sprache:
Englisch
Verlag:
Wiley
Publikationsdatum:
2020
ZDB Id:
2011836-3
ZDB Id:
123227-7