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Accessing iron amides from dimesityliron

Journal article
Authors J. Sundberg
M. S. Vad
J. E. McGrady
Per Martin Björemark
Mikael Håkansson
C. J. McKenzie
Published in Journal of Organometallic Chemistry
Volume 786
Pages 40-47
ISSN 0022-328X
Publication year 2015
Published at Department of Chemistry and Molecular Biology
Pages 40-47
Language en
Links dx.doi.org/10.1016/j.jorganchem.201...
Keywords Iron, Mesityl, Amide, METAL ATOM CHAINS, THEORETICAL-ANALYSIS, MAGNETIC-PROPERTIES, CRYSTAL-STRUCTURE, AXIAL LIGAND, COMPLEXES, CHEMISTRY, BONDS, ENERGY, TETRAMESITYLDIIRON, Chemistry, Inorganic & Nuclear, Chemistry, Organic
Subject categories Organic Chemistry

Abstract

A new phase of dimesityliron has been crystallized from diethylether; the crystal structure shows a dinuclear complex with co-crystallized solvent. Crystalline [Fe-2(mes)(2)(mu(2)-mes)(2)]center dot Et2O is a convenient starting material and reacts with di(2-pyridyl) amine to yield rare iron di(2-pyridyl) amido complexes. Crystal structures of air-sensitive [Fe-2(mes)(2)(dpa)(2)], [Fe-2(dpa)(3)Cl] and [Fe-4(dpa)(6)O] were determined. [Fe-4(dpa)(6)O] is known, and the dinuclear complexes [Fe-2(mes)(2)(dpa)(2)] and [Fe-2(dpa)(3)Cl] represent only the second and third reports of homometallic iron dpa(-) complexes. Long Fe. Fe distances of 3.043(1) and 3.104(2) angstrom in [Fe-2(mes)(2)(dpa)(2)] and [Fe-2(dpa)(3)Cl], respectively, and very unsymmetrically coordinated amido groups, indicate that the iron atoms are not involved in M-M bonding. This fact, and the relatively low coordination numbers of the high spin Fe(II) atoms are consistent with sensitivity of these compounds towards O-2. DFT calculations were employed to rationalize the formation of the unusual architectures displayed by the dpa(-) complexes of iron. (C) 2015 Elsevier B.V. All rights reserved.

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