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Preparation of 6-aminocyclohepta-2,4-dien-1-one Derivatives via Tricarbonyl(tropone)iron
Published on: August 12, 2019
Two-step spin-transition iron(III) compound with a wide [high spin-low spin] plateau
Jinkui Tang1, José Sánchez Costa, Simon Smulders
1Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
Abstract:
A new iron(III) coordination compound exhibiting a two-step spin-transition behavior with a remarkably wide [HS-LS] plateau of about 45 K has been synthesized from a hydrazino Schiff-base ligand with an N,N,O donor set, namely 2-methoxy-6-(pyridine-2-ylhydrazonomethyl)phenol (Hmph). The single-crystal X-ray structure of the coordination compound {[Fe(mph)(2)](ClO(4))(MeOH)(0.5)(H(2)O)(0.5)}(2) (1) determined at 150 K reveals the presence of two slightly different iron(III) centers in pseudo-octahedral environments generated by two deprotonated tridentate mph ligands. The presence of hydrogen bonding interactions, instigated by the well-designed ligand, may justify the occurrence of the abrupt transitions. 1 has been characterized by temperature-dependent magnetic susceptibility measurements, EPR spectroscopy, differential scanning calorimetry, and (57)Fe Mossbauer spectroscopy, which all confirm the occurrence of a two-step transition. In addition, the iron(III) species in the high-spin state has been trapped and characterized by rapid cooling EPR studies.
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