N−H Bond Formation at a Diiron Bridging Nitride

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.

Covalent Labeling with Diethylpyrocarbonate: Sensitive to the Residue Microenvironment, Providing Improved Analysis of Protein Higher Order Structure by Mass Spectrometry

“…The differential reactivity of proteins under different conditions can be used to distinguish and deduce protein conformations, topologies, and/or binding sites. Common applications of CL-MS techniques include protein folding/unfolding, [1][2][3][4] amyloid-forming proteins, [5][6][7][8][9] protein-ligand systems, [10][11][12][13] and structural analysis of protein therapeutics, [14][15][16][17][18][19] among others. Several review articles are dedicated to these relatively new MS-based structural techniques.…”