کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1309553 | 975213 | 2009 | 7 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: A high-spin Fe(II)/low-spin Fe(III) redox couple featuring the hydro[tris(4-chloro-3,5-dimethyl-pyrazolyl)]borate ligand: Synthesis, spectroscopic and X-ray crystallographic characterization A high-spin Fe(II)/low-spin Fe(III) redox couple featuring the hydro[tris(4-chloro-3,5-dimethyl-pyrazolyl)]borate ligand: Synthesis, spectroscopic and X-ray crystallographic characterization](/preview/png/1309553.png)
The white homoleptic high-spin iron(II) complexes Fe[TpMe2,4Cl]2 (1) was isolated in quantitative yield from reaction mixtures containing 1 equiv of FeCl2(THF)1.5 and 2 equiv of K[TpMe2,4Cl] (TpMe2,4Cl = hydrotris[(4-chloro-3,5-dimethyl-pyrazolyl)]borate). Its purple low-spin iron(III) counterparts 1[O3SCF3] and 1[PF6] were synthesized and isolated in 85% yields upon treatment of 1 with 1 equiv of silver triflate and silver hexafluorophosphate, respectively. The three paramagnetic compounds are air and thermally stable as solids and in solution; they were characterized by elemental analyses, IR, magnetic susceptibility measurements, 1H NMR, and Mössbauer spectroscopy. In addition, 1[PF6] was authenticated by a single-crystal X-ray diffraction. The two scorpionate ligands are κ3-N,N′,N′′ ligated to the central FeIII ion, forming an almost perfect FeN6 octahedron with an average Fe–N bond distance of 1.9551(18) Å. In addition, complex 1 which oxidizes reversibly at E1/2 = 0.483 V/SCE (ΔEp = 94 mV), remains high-spin (S = 2) when the temperature is lowered to 2 K.
The high-spin bis(scorpionate)iron(II) complexes Fe[TpMe2,4Cl]2 (1) And its low-spin iron(III) counterparts 1[O3SCF3] and 1[PF6] were synthetized and isolated in high yields. Complex 1 remains high-spin when the temperature is lowered to 2 K, and its FeII/FeIII oxidation potential is approximately 0.5 V more positive than for Fe[TpMe2]2.Figure optionsDownload as PowerPoint slide
Journal: Inorganica Chimica Acta - Volume 362, Issue 12, 15 September 2009, Pages 4389–4395