Synthesis,Structure, and Characterization of [FeIIILCl3] (L = 1, 4, 8‐Triazacycloundecane, 1, 4, 7‐Triazacyclononane) |
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| Authors: | Atanu Banerjee Manashi Panda Azam S Tolla Jia Li William W Brennessel Reza Loloee Prof Dr Ferman A Chavez |
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| Institution: | 1. Department of Chemistry, Oakland University, Rochester, MI 48309–4477, USA;2. Department of Chemistry, University of Rochester, Rochester, NY 14627–0216, USA;3. Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824–1322, USA |
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| Abstract: | The structures of FeIII(tacud)Cl3] ( 1 ) and FeIII(tacn)Cl3] ( 2 ) (tacud = 1, 4, 8‐triazacycloundecane, tacn = 1, 4, 7‐triazacyclononane) are reported. Both compounds crystallize in the orthorhombic space group Pnma with a = 12.5570(9), b = 12.0028(9), c = 8.2577(6) Å, V = 1244.59(16) Å3, and Z = 4 for 1 and a = 12.095(4), b = 11.125(4), c = 7.963(3) Å, V = 1071.5(6) Å3, and Z = 4 for 2 . The structures of 1 and 2 feature iron(III) in distorted octahedral arrangement with three facially coordinated nitrogen ligands and three chlorides. Bidirectional intermolecular hydrogen bonding between N–H groups and coordinated chlorides is seen for 1 and 2 . Compound 1 is the first example of iron(III) bonded to tacud and compound 2 is only the second structure reported of a 1:1 complex between iron and tacn. The Fe3+/2+ redox couple for 1 is observed at E1/2 = 0.25 V (ΔEp = 99 mV), and for 2 at E1/2 = 0.09 V (ΔEp = 108 mV) versus NHE in DMF at 298 K. Comparison of structural, magnetic, and electrochemical properties for 1 and 2 reveal subtle differences consistent with the stronger coordinating properties of tacn relative to tacud. |
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| Keywords: | Macrocyclic ligands Iron Cyclic voltammetry Magnetic properties |
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