In:
Angewandte Chemie, Wiley, Vol. 132, No. 35 ( 2020-08-24), p. 15327-15331
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:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v132.35
DOI:
10.1002/ange.202006391
Sprache:
Englisch
Verlag:
Wiley
Publikationsdatum:
2020
ZDB Id:
505868-5
ZDB Id:
506609-8
ZDB Id:
514305-6
ZDB Id:
505872-7
ZDB Id:
1479266-7
ZDB Id:
505867-3
ZDB Id:
506259-7