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• W2034307691 abstract "Electronic structures of five- and six-coordinate iron(III) corrolazine complexes are determined by means of 1 H NMR, 13 C NMR, EPR, and Mössbauer spectroscopy as well as SQUID magnetometry. A series of five-coordinate complexes, [Fe III (TBP 8 Cz)(L)]* where the axial ligands(L) are cyanide(CN - ), imidazole(HIm), 1-methylimidazole(1-MeIm), 4-(N,N-dimethylamino)pyridine(DMAP), pyridine(Py), 4-cyanopyridine(4-CNPy), and tert-butylisocyanide( t BuNC), are obtained by the addition of 1 to 2 equiv. of the ligands to the dichloromethane solutions of Fe III (TBP 8 Cz) at 298 K: TBP 8 Cz is a trianion of 2,3,7,8,12,13,17,18-octakis(4-tert-butylphenyl)corrolazine. These complexes commonly show the S = 3/2 at 298 K. By contrast, formation of the six-coordinate complexes depends on the nature of the axial ligands. While the addition of 3 equiv. of CN - has completely converted Fe III (TBP 8 Cz) to (Bu 4 N) 2 [Fe III (TBP 8 Cz)(CN) 2 ] at 298 K, the conversion to the bis-adduct is only attained below ca. 200 K in the case of HIm, 1-MeIm, and DMAP even in the presence of 50 equiv. of the ligands. If the axial ligand is Py, 4-CNPy, or t BuNC, the formation of [Fe III (TBP 8 Cz)(L) 2 ] is confirmed only at an extremely low temperature (15 K). Close inspection of the 1 H NMR and EPR spectra has revealed that all the bis-adducts adopt the (d xy ) 2 (d xz , d yz ) 3 ground state. While Fe III (TBP 8 Cz) forms paramagnetic bis- and mono-adduct in toluene solution at 298 K in the presence of excess amount of CN - and t BuNC, respectively, the corresponding porphyrazine complex, [Fe III (TBP 8 Pz)]Cl , forms diamagnetic bis-CN and bis- t BuNC under the same conditions: TBP 8 Pz is a dianion of 2,3,7,8,12,13,17,18-octakis(4-tert-butylphenyl)-porphyrazine. Thus, the iron(III) ion of porphyrazine complex is more easily reduced than that of the corresponding corrolazine complex." @default.
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• W2034307691 date "2012-05-01" @default.
• W2034307691 modified "2023-09-27" @default.
• W2034307691 title "Formation and characterization of five- and six-coordinate iron(III) corrolazine complexes" @default.
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• W2034307691 doi "https://doi.org/10.1142/s1088424612500460" @default.
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