Synthesis, structure, and reactivity of an iron(V) nitride.

Jeremiah J Scepaniak, Carola S Vogel, Marat M Khusniyarov, Frank W Heinemann, Karsten Meyer, Jeremy M Smith

Department of Chemistry and Biochemistry, MSC 3C, New Mexico State University, Las Cruces, NM 88003, USA.

Science (New York, N.Y.) 2011 Feb 25

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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((t)BuIm)(3)Fe(V)≡N]BAr(F24) (PhB((t)BuIm)(3)(-) = phenyltris(3-tert-butylimidazol-2-ylidene)borato, BAr(F24) = B(3,5-(CF(3))(2)C(6)H(3))(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 d(3) 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.

Citation

Jeremiah J Scepaniak, Carola S Vogel, Marat M Khusniyarov, Frank W Heinemann, Karsten Meyer, Jeremy M Smith. Synthesis, structure, and reactivity of an iron(V) nitride. Science (New York, N.Y.). 2011 Feb 25;331(6020):1049-52