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The interaction of the antitumor agent daunomycin (DN) with ferric iron has been analysed by Mōssbauer spectroscopy, EPR, extended X-ray absorption fine structure (EXAFS), and magnetic susceptibility measurements. In contrast to literature data, at millimolar iron and anthracycline concentrations no solitary Fc(DN)3 complexes are formed in appreciable amounts. The Mössbauer spectroscopic analysis revealed severe dependencies on temperature, on the preparation procedure, the time allowed for equilibration, and on the metal/ligand ratio. The Mössbauer spectra exhibit two components: a broad magnetic sextet and a quadrupole doublet at an Fe/DN molar ratio of 1:3 and exclusively a doublet at a molar ratio of 1:20, indicating an equilibrium of these two spectral components. The EPR spectra are dominated by a signal at geff = 2. Double integration of the EPR signals enabled the determination of their spin density and a correlation between EPR and Mössbauer spectra. The Mössbauer sextet species is EPR invisible and corresponds to magnetically ordered polynuclear aggregates with high magnetic anisotropy. EXAFS and susceptibility measurements provide additional evidence for the formation of polynuclear aggregates of ferric daunomycin. The quadrupole doublet species in the Mössbauer spectra correlates with the g = 2 signal in EPR. This species is also related to a magnetically ordered system, exhibiting, however, superparamagnetic behavior due to less magnetic anisotropy. Since daunomycin forms dimers in aqueous solution at millimolar concentrations, we conclude that the cooperative phenomena observed in EPR and Mössbauer spectra are a consequence of its stacking effects. [ABSTRACT FROM AUTHOR]

Two dioxygen adducts of thiolato‐iron(II) porphyrins, [K(⊂ 222)][Fe(TPpivP)(SC6HF4)(O2)] 1a and [Na(⊂ 18c.6)][Fe(TPpivP)(SC6HF4)(O2)] 2 were synthesized by reaction of O2 with five‐coordinate, high‐spin, cryptated alkali metal thiolato‐iron(II) ‘picket fence’ porphyrinate. They were characterized by visible and infrared spectroscopy: λmax (log ɛ) = 360 nm (4), 427 nm (4.69), 560 nm (3.69), 610 nm (3.40) for both compounds; v(16O‐16O) = 1139 cm−1 in chlorobenzene and fluorobenzene for 1a and 2. Single crystals of composition [K(⊂ 222)][Fe(TPpivP)(SC6HF4)(O2)] · [K(⊂ 222)](SC6HF4)(C6H5Cl)(H2O) 1b were obtained by diffusion of pentane/xylene mixtures into chlorobenzene solutions of 1a at – 5°C. Single crystals of composition [Na(⊂ 18c.6)][Fe(TPpivP)(SC6HF4)(O2)] were obtained by slow diffusion of pentane into benzene solutions of 2. Structures of 1b and 2 were studied at 20°C (1b) and – 100°C (1b and 2). 1b: space group P21/c (monoclinic), a= 16.806(5) Å (1.6806 nm), b= 14.331(4) Å (1.4331 nm), c= 52.000(15) Å (5.2000 nm), β= 92.95(2)°, V= 12507 Å3 (12.507 nm3), Z= 4, Dcal= 1.28 g · cm−3 (t= 20°C). The final R1 factor was 0.085 for 5238 reflections having I > 3 σ(I). 2: space group P21/c (monoclinic), a= 13.107(3) Å (1.3107 nm), b= 27.055(4) Å (2.7055 nm), c= 25.029(4) Å (2.5029 nm), β= 96.84(2)°, V= 8812 Å3 (8.812 nm3), Z= 4, Dcal= 1.18 g · cm−3 (t=−100°C). The final R1 factor was 0.088 for 6587 reflections having I > 3 σ(I). The iron atom is, in both compounds, bonded to the four porphyrinato nitrogens (Np), the sulfur atom of the axial thiolate and one oxygen atom of the axially end‐on bonded dioxygen molecule. The average Fe‐Np distance found in 1b [1.994(4) Å, 0.1994 nm] is not significantly different from that found in 2 [1.993(3) Å, 0.1993 nm]. The Fe‐S bond length is 2.367(3) Å (0.2367 nm) in 1b and 2.365(2) Å (0.2365 nm) in 2. The Fe‐O1 distances with the oxygen atom of O2 bonded to iron are respectively 1.837(9) Å (0.1837 nm) and 1.850(4) Å (0.1850 nm). The end‐on bonded O2 molecule is disordered in both complexes 1b and 2. This disorder is, however, slightly different from one structure to the other. Whereas the terminal oxygen atom of O2 occupies two positions in 1b [τ(O2A) = 78%, τ(O2B) = 22% at 20°C], it occupies three sites in 2 [τ(O2A) = 51%, τ(O2B) =τ(O2C) = 24.5% at – 100°C] (τ= occupancy). The estimate of the magnitude of the non‐bonded interactions between O2 and its environment located in a sphere of 7‐Å (0.7‐nm) radius in 1b and 2 is consistent with a static disorder of O2 in 1b and a dynamic distribution in 2. Mössbauer measurements were performed with polycrystals of 1b and 2 in the temperature ranges 5 – 197 K and 4.2 – 295 K, respectively, and under externally applied magnetic field (6.76 T) at 4.2 K (1b and 2) and at 173 K (2). The temperature variation of the Lamb‐Mössbauer factor indicates that the iron atom in these oxycytochrome P450 models is not very firmly bonded, more like that in pentacoordinated than in other hexacoordinated hemes. From the specific temperature behavior of quadrupole splitting, asymmetry parameter and line width obtained for 2, the structural disorder of the terminal oxygen atom of O2 is identified as dynamic distribution over three different sites. Corresponding values obtained for 1b are consistent with a static disorder of O2. Magnetic spectra reveal that the oxycytochrome P450 models are purely diamagnetic. [ABSTRACT FROM AUTHOR]