Pyrazolyl Methyls Prescribe the Electronic Properties of Iron(II) Tetra(pyrazolyl)lutidine Chloride Complexes


A series of iron(ii) chloride complexes of pentadentate ligands related to α,α,α',α'-tetra(pyrazolyl)-2,6-lutidine, pz 4lut, 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 CoCl 2-catalyzed rearrangement reaction. The equimolar combination of ligand and FeCl 2 in methanol gives the appropriate 1:1 complexes [FeCl(pz R 4lut)]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.



Keywords and Phrases

Chloride Complexes; High Spins; Inductive Effects; Iron Chlorides; Iron Complex; Ligand Field; Lutidine; Mössbauer; Pyrazolyl; Rearrangement Reactions; Spectroscopic Method; Spin-state; Ssbauer Spectroscopies; Steric Effect; Structural Studies; Tetrakis; Thermochromic Properties; Chlorine Compounds; Cyclic Voltammetry; Driers (Materials); Electronic Properties; Iron; Ligands; Methanol; Molybdenum Compounds; Spectroscopic Analysis; X Ray Diffraction; Iron Compounds; 2,6 Lutidine N Oxide; 2,6-lutidine N-oxide; Amine Oxide; Iron; Methanol; Organometallic Compound; Pyrazole Derivative; Chemical Structure; Chemistry; Electrochemistry; X Ray Diffraction; Cyclic N-Oxides; Electrochemistry; Iron; Methanol; Molecular Structure; Organometallic Compounds; Pyrazoles; X-Ray Diffraction

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