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The Royal Society of Chemistry
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A series of iron(II) chloride complexes of pentadentate ligands related to α,α,α′,α′-tetra(pyrazolyl)-2,6-lutidine, pz4lut, has been prepared to evaluate whether pyrazolyl substitution has any systematic impact on the electronic properties of the complexes. For this purpose, the new tetrakis(3,4,5-trimethylpyrazolyl)lutidine ligand, pz**4lut, was prepared via a CoCl2-catalyzed rearrangement reaction. The equimolar combination of ligand and FeCl2 in methanol gives the appropriate 1:1 complexes [FeCl(pzR4lut)]Cl that are each isolated in the solid state as a hygroscopic solvate. In solution, the iron(II) complexes have been fully characterized by several spectroscopic methods and cyclic voltammetry. In the solid state, the complexes have been characterized by X-ray diffraction, and, in some cases, by Mössbauer spectroscopy. The Mössbauer studies show that the complexes remain high spin to 4 K and exclude spin-state changes as the cause of the surprising solid-state thermochromic properties of the complexes. Non-intuitive results of spectroscopic and structural studies showed that methyl substitution at the 3- and 5- positions of the pyrazolyl rings reduces the ligand field strength through steric effects whereas methyl substitution at the 4-position of the pyrazolyl rings increases the ligand field strength through inductive effects.
Morin, Tyler James; Wanniarachchi, Sarath; Gwengo, Chengeto; Makura, Vitales; Tatlock, Heidi M.; Lindeman, Sergey; Bennett, Brian; Long, Gary J.; Grandjean, Fernande; and Gardinier, James R., "Pyrazolyl Methyls Prescribe the Electronic Properties of Iron(II) Tetra(pyrazolyl)lutidine Chloride Complexes" (2011). Physics Faculty Research and Publications. 49.