Year: 2025
Type: article
Abstract: Transition metal nitrides are reactive intermediates in biological and industrial processes. Chemists have synthesized molecular model complexes of such reactive species to understand their function and electronic requirements for new applications. However, molecular chemistry can suffer from intra- and intermolecular decomposition pathways, which preclude further discovery of unknown reactive species. Metal–organic frameworks offer an opportunity for creating long-lived forms of such species with the vacuum of the pore suppressing degradation while simultaneously enabling substrate access for controlled reactivity studies. Here, we report the characterization of an elusive terminal cobalt nitride species generated through photolysis or thermolysis of a site-isolated cobalt azide within the evacuated metal–organic framework CoN 3 -MFU-4 l . The first crystal structure of such a species is presented, with vibrational, X-ray absorption, and electron paramagnetic resonance spectroscopies providing further direct evidence for its formation while elucidating its electronic structure. The system additionally enables subsequent reactivity studies with selected substrates, revealing a unique ambiphilic behavior for a metal nitride species.
DOI: 10.1021/jacs.5c16444
Authors: Jonas Börgel, Nicole Removski, Jordan W. Taylor, Zikri Hasanbasri, Khetpakorn Chakarawet, Alexander J. Heyer, Patrick W. Smith, N. Isaac Zakaria, Danh X. Ngo, Ryan A. Klein, Maria V. Paley, Vincent R. Allen, Chaochao Dun, Henry Z. H. Jiang, Nykita Z. Rustad, Tieyan Chang, Ying-Pin Chen, Mauricio Lopez Luna, Wanli Yang, Brandon R. Barnett, Jeffrey A. Reimer, Yu-Sheng Chen, Jeffrey J. Urban, Monika Blum, Stefan G. Minasian, Edward I. Solomon, R. David Britt, T. David Harris, Jeffrey R. Long
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Funders: National Science Foundation, Adolph C. and Mary Sprague Miller Institute for Basic Research in Science, University of California Berkeley, National Institutes of Health, Office of Science, National Defense Science and Engineering Graduate, Basic Energy Sciences, Army Research Office, Argonne National Laboratory, Advanced Light Source
Awards: Acquisition of a Cryoprobe and Related Accessories for a 600 MHz NMR Spectrometer to Support Health Research Activities at the University of California, Berkeley, G1147409705, G2638771445, G2759181536, G3504934782, High Performance Computing Cluster for Public Health Driven Molecular Science - Core Facility, G419881185, MRI: Acquisition of a 400 MHz Nuclear Magnetic Resonance (NMR)Spectrometer to Enable Material Science Research, G9000169178, G9000202912
OpenAlex ID: W7116675280