1. N−H Bond Formation at a Diiron Bridging Nitride.
- Author
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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., and Tomson, Neil C.
- Subjects
CHARGE exchange ,CHEMICAL yield ,NITRIDES ,PROTON transfer reactions ,NITRIDING ,SILYL ethers ,AMMONIA - 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 NH3 in high yield through a reaction that engages the redox‐activity of the ligand during PCET. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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