TY - JOUR
T1 - Pyrazolyl methyls prescribe the electronic properties of iron(ii) tetra(pyrazolyl)lutidine chloride complexes
AU - Morin, Tyler J.
AU - Wanniarachchi, Sarath
AU - Gwengo, Chengeto
AU - Makura, Vitales
AU - Tatlock, Heidi M.
AU - Lindeman, Sergey V.
AU - Bennett, Brian
AU - Long, Gary J.
AU - Grandjean, Fernande
AU - Gardinier, James R.
PY - 2011/8/21
Y1 - 2011/8/21
N2 - 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.
AB - 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.
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U2 - 10.1039/c1dt10712g
DO - 10.1039/c1dt10712g
M3 - Article
C2 - 21720641
AN - SCOPUS:79960914956
SN - 1477-9226
VL - 40
SP - 8024
EP - 8034
JO - Dalton Transactions
JF - Dalton Transactions
IS - 31
ER -