Publication Date:
2011-02-26
Description:
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) identical withN]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. Mossbauer 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.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Scepaniak, Jeremiah J -- Vogel, Carola S -- Khusniyarov, Marat M -- Heinemann, Frank W -- Meyer, Karsten -- Smith, Jeremy M -- New York, N.Y. -- Science. 2011 Feb 25;331(6020):1049-52. doi: 10.1126/science.1198315.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry and Biochemistry, MSC 3C, New Mexico State University, Las Cruces, NM 88003, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/21350172" target="_blank"〉PubMed〈/a〉
Keywords:
Crystallization
;
Crystallography, X-Ray
;
Electron Spin Resonance Spectroscopy
;
Ferric Compounds/chemical synthesis/*chemistry
;
Iron/*chemistry
;
Ligands
;
Molecular Structure
;
Nitrogen/chemistry
;
Oxidation-Reduction
;
Physicochemical Processes
;
Spectroscopy, Mossbauer
Print ISSN:
0036-8075
Electronic ISSN:
1095-9203
Topics:
Biology
,
Chemistry and Pharmacology
,
Computer Science
,
Medicine
,
Natural Sciences in General
,
Physics
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