Formation and characterization of five- and six-coordinate iron(III) corrolazine complexes

Abstract

Electronic structures of five- and six-coordinate iron(III) corrolazine complexes are determined by means of1H NMR,13C NMR, EPR, and Mössbauer spectroscopy as well as SQUID magnetometry. A series of five-coordinate complexes, [FeIII(TBP8Cz)(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(tBuNC), are obtained by the addition of 1 to 2 equiv. of the ligands to the dichloromethane solutions of FeIII(TBP8Cz) at 298 K: TBP8Cz 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 FeIII(TBP8Cz) to (Bu4N)2[FeIII(TBP8Cz)(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, ortBuNC, the formation of [FeIII(TBP8Cz)(L)2] is confirmed only at an extremely low temperature (15 K). Close inspection of the1H NMR and EPR spectra has revealed that all the bis-adducts adopt the (dxy)2(dxz, dyz)3ground state. While FeIII(TBP8Cz) forms paramagnetic bis- and mono-adduct in toluene solution at 298 K in the presence of excess amount of CN-andtBuNC, respectively, the corresponding porphyrazine complex, [FeIII(TBP8Pz)]Cl , forms diamagnetic bis-CN and bis-tBuNC under the same conditions: TBP8Pz 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.