1. N-H Bond Formation at a Diiron Bridging Nitride.
- Author
-
Zhang S, Cui P, Liu T, Wang Q, Longo TJ, Thierer LM, Manor BC, Gau MR, Carroll PJ, Papaefthymiou GC, and Tomson NC
- Subjects
- Hydrogen Bonding, Oxidation-Reduction, Electron Transport physiology, Nitrogen chemistry
- Abstract
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., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)- Published
- 2020
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