Mononuclear and dinuclear iron thiocyanate and selenocyanate complexes of tris-pyrazolylmethane ligands |
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| Authors: | A Abibat Salaudeen Colin A KilnerMalcolm A Halcrow |
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| Institution: | School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK |
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| Abstract: | Treatment of Fe(NCE)2 (E = S or Se) with 1 equiv. of tris-(3,5-dimethylpyrazol-1-yl)methane (tpm′) yields dimeric {Fe(NCE)(μ-NCE)(tpm′)}2]. These dimers are cleaved in MeCN solution, yielding isolable Fe(NCE)2(tpm′)(NCMe)], whose solvent ligands can be substituted by moderately basic heterocycle donors to give Fe(NCE)2(tpm′)(py)], Fe(NCS)2(tpm′)(im)] or {Fe(NCE)2(tpm′)}2(μ-4,4′-bipy)]. The monodentate heterocycles in the latter compounds are readily lost in most solvents, regenerating the dimeric starting materials. Fe(NCS)2(tpm′)(py)] was also prepared by reacting Fe(NCS)2(py)4] with tpm′. The mononuclear compounds are all high-spin between 5 and 300 K, despite mostly having regular coordination geometries and tpm′ ligand conformations that should in principal favour spin-crossover. Analogous products containing unsubstituted tris-(pyrazol-1-yl)methane (tpm) could not be isolated, but the crystal structure of the double salt Fe(tpm)2]Fe(NCS)5(py)], containing a new iron(III) anion, is described. |
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| Keywords: | Iron Dinuclear complexes Crystal structure Magnetic properties |
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