Structural diversity in iron(II) complexes of 2,6-di(pyrazol-1-yl)pyridine and 2,6-di(3-methylpyrazol-1-yl)pyridine |
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Authors: | Elhaïk Jérôme Kilner Colin A Halcrow Malcolm A |
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Institution: | School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, UK LS2 9JT. |
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Abstract: | The syntheses, magnetochemistry and crystallography of Fe(L1)2]I0.5I3]1.5 (1), Fe(L1)2]Co(C2B9H11)2]2 (2) and Fe(L2)2]SbF6]2 (3) (L1 = 2,6-di(pyrazol-1-yl)pyridine; L2 = 2,6-di(3-methylpyrazol-1-yl)pyridine) are described. Compounds 1 and 3 are high-spin between 5-300 K. For 1, this reflects a novel variation of an angular Jahn-Teller distortion at the iron centre, which traps the molecule in its high-spin state. No such distortion is present in 3; rather, the high-spin nature of this compound may reflect ligand conformational strain caused by an intermolecular steric contact in the crystal lattice. Compound 2 exhibits a gradual high --> low spin transition upon cooling with T(1/2) = 318 +/- 3 K, that is only 50% complete. This reflects the presence of two distinct, equally populated iron environments in the solid. One of these unique iron centres adopts the same angular structural distortion shown by 1 and so is trapped in its high-spin state, while the other, which undergoes the spin-crossover, has a more regular coordination geometry. In contrast with 3, the solvated salts Fe(L2)2]BF4]2 x 4 CH3CN and Fe(L2)2]ClO4]2 x (CH3)2CO both undergo gradual thermal spin-transitions centred at 175 +/- 3 K. |
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