Synthesis of Chromium(IV) Nitrides Through High-Spin Tetrahedral Chromium(I) Intermediates
Grace B. Panetti, Matthew V. Pecoraro, Runzi Li, Junho Kim, Gabriele Hierlmeier, Paul J. Chirik
TL;DR
Scientists synthesized chromium(IV) nitrides using high-spin tetrahedral chromium(I) intermediates, revealing unique chemical properties and synthesis challenges.
Contribution
The paper reports the first synthesis of chromium(IV) nitrides via high-spin tetrahedral chromium(I) intermediates.
Findings
Chromium(I) dinitrogen complexes were formed under nitrogen gas.
Chromium(IV) nitrides were confirmed using spectroscopy and X-ray crystallography.
The nitrides showed limited reactivity toward H2 and diphenylsilane.
Abstract
Reduction of (depe)2CrCl2 (depe = 1,2-bis(diethylphosphino)ethane) and (dep-benz)2CrCl2 (dep-benz = 1,2-bis(diethylphosphino)benzene) under 1 atm of N2 furnished the dinitrogen complexes (depe)2Cr(N2)2 and (dep-benz)2Cr(N2)2, respectively. One-electron oxidation of these products with FcBArF 4 (Fc = ferrocenium, BArF 4 = B(3,5-(CF3)2C6H3)4) yielded the unusual, high-spin tetrahedral complexes [(depe)2Cr][BArF 4] and [(dep-benz)2Cr][BArF 4] with concomitant loss of dinitrogen. Reaction of the chromium(I) derivatives with Ph3CN3 furnished rare examples of chromium(IV) nitrides as confirmed spectroscopically and by X-ray crystallography. While [(depe)2Cr(N)][BArF 4] underwent association of isocyanides accompanied by partial ligand dissociation, neither chromium nitride was reactive toward H2 or diphenylsilane under thermal or photochemical conditions. These results distinguish…
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Taxonomy
TopicsOrganometallic Complex Synthesis and Catalysis · Magnetism in coordination complexes · Boron Compounds in Chemistry