Synthesis, Structure, and Reactivity of an Iron(V) Nitride
- 25 February 2011
- journal article
- other
- Published by American Association for the Advancement of Science (AAAS) in Science
- Vol. 331 (6020), 1049-1052
- https://doi.org/10.1126/science.1198315
Abstract
Despite being implicated as important intermediates, iron(V) compounds have proven very challenging to isolate and characterize. Here, we report the preparation of the iron(V) nitrido complex, [PhB(tBuIm)3FeV≡N]BArF24 (PhB(tBuIm)3– = phenyltris(3-tert-butylimidazol-2-ylidene)borato, BArF24 = B(3,5-(CF3)2C6H3)4–), by one electron oxidation of the iron(IV) nitrido precursor. Single-crystal x-ray diffraction of the iron(V) complex reveals a four-coordinate metal ion with a terminal nitrido ligand. Mößbauer and electron paramagnetic resonance spectroscopic characterization, supported by electronic structure calculations, provide evidence for a d3 iron(V) metal center in a low spin (S = 1/2) electron configuration. Low-temperature reaction of the iron(V) nitrido complex with water under reducing conditions leads to high yields of ammonia with concomitant formation of an iron(II) species.Keywords
Funding Information
- Office of Basic Energy Sciences (DE-FG02-08ER15996)
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