title: Synthesis, structure, and reactivity of an iron(V) nitride.
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((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.
authors.affiliation: Department of Chemistry and Biochemistry, MSC 3C, New Mexico State University, Las Cruces, NM 88003, USA.
authors.forename: Jeremiah J
authors.initials: JJ
authors.lastname: Scepaniak
authors.forename: Carola S
authors.initials: CS
authors.lastname: Vogel
authors.forename: Marat M
authors.initials: MM
authors.lastname: Khusniyarov
authors.forename: Frank W
authors.initials: FW
authors.lastname: Heinemann
authors.forename: Karsten
authors.initials: K
authors.lastname: Meyer
authors.forename: Jeremy M
authors.initials: JM
authors.lastname: Smith
mesh_terms: D055598:Chemical Phenomena; D003460:Crystallization; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D005290:Ferric Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry; D010084:Oxidation-Reduction; D015204:Spectroscopy, Mossbauer
chemical_list: D005290:Ferric Compounds; D008024:Ligands; C540999:iron nitrido complex; C066318:perferryl iron; D007501:Iron; D009584:Nitrogen