The chloroiron(III) complex of 2,8,12,18-tetrabutyl-3,7,13,17-tetramethyl-5,10-diazaporphyrin, [(Cl)FeMBDAP], was prepared and studied by X-ray crystallography and by solution (1)H NMR and UV-vis measurements. In the crystal structure of hemisolvate [(Cl)FeMBDAP] x 0.5CHCl(3), two nonequivalent [(Cl)FeMBDAP] units containing Fe1 and Fe2 are arranged in pi-dimers with considerable overlap on their concave sides. Axial chloride bonded to Fe2 is solvated by hydrogen bonding with CHCl(3). Parameters of the coordination pyramid have typical values for the spin-mixed (S = 3/2 / 5/2) Fe(III) complexes in the case of Fe1 and are characteristic for the pure intermediate-spin state for Fe2 (displacement from the (N(Pyr))(4) planes - 0.385 and 0.290 A and the average N(Pyr)-Fe bond lengths -1.992 and 1.954 A for Fe1 and Fe2, respectively). Effective magnetic moments in CHCl(3) and CH(2)Cl(2) capable of specific solvation of chloride by hydrogen bonding (4.5-4.6 micro(B) at 298 K) are indicative about mixed intermediate/high-spin state S = 3/2 / 5/2, with the S = 3/2 contribution increasing upon lowering of the temperature (4.02 micro(B) in CD(2)Cl(2) at 193 K). In nonsolvating CCl(4), C(6)D(6), and THF-d(8), the mu(eff) values are consistent with the predominantly high-spin state at ambient temperature (5.5-5.75 micro(B) at 298 K) and almost pure S = 5/2 state at low temperature (ca. 5.9 micro(B) in THF-d(8) below 270 K). Downfield isotropic shifts from 35 to 50 ppm are observed for alpha-alkyl protons and upfield shifts from -5 to -15 ppm for meso-CH protons, which is characteristic for the presence of the intermediate-spin state. The splitting of signals of the diastereotopic alpha-CH(2) protons is increased with growth of the S = 3/2 state contribution from 1.5 to 4 ppm in nonsolvating to 11 ppm in specifically solvating solvents at 298 K and further to 31 ppm at 193 K (in CD(2)Cl(2)). In the presence of DMSO addition and in methanol solution, the single CH(2) signal is observed at 25-28 ppm, and the meso-CH resonance is also shifted downfield to ca. 30 ppm, indicating the formation of six-coordinated complexes [(DMSO)(2)FeMBDAP](+) and [(MeOH)(2)FeMBDAP](+), the latter having the mu(eff) value of 4.92 micro(B) at 291 K is a spin-mixed species. The electron spin resonance spectra recorded at 77 K indicates that in frozen glasses in CD(2)Cl(2) and THF molecules in the high-spin state (g( perpendicular) approximately 6) and the predominantly intermediate-spin state (g( perpendicular) approximately 4.2-4.3) coexist together.

Binuclear μ‐oxo‐bridged FeIII complexes of 2,3,7,8,12,18‐hexamethyl‐13,17‐dibutyl‐5‐monoazaporphine [μ‐O(FeMAP)2], and 3,7,13,17‐tetramethyl‐2,8,12,18‐tetrabutyl‐5,15‐diazaporphine [μ‐O(FeDAP)2] have been prepared and characterised using UV/Vis, IR and 1H NMR spectroscopies. The stretching vibrations of the μ‐oxo‐bridge νas(Fe–O–Fe) are observed at 880 cm–1 for μ–O(FeMAP)2 and at 871 cm–1 for μ‐O(FeDAP)2. The structure of μ‐O(FeDAP)2 has been confirmed by the single‐crystal X‐ray diffraction study of its monobenzene solvate. The Fe1 and Fe2 atoms are displaced from the mean planes formed by the coordinating N‐atoms by 0.572 and 0.565 Å, respectively, and are connected to one another through the μ‐oxo‐bridge. The average Fe1–N and Fe2–N bond lengths are 2.053 and 2.050 Å, and the Fe1–O and Fe2–O bond lengths are 1.777 and 1.776 Å, respectively. The Fe1–O–Fe2 angle is 152.1°, which leads to a non‐coplanar arrangement of the two adjacent macrocyclic units (tilt angle 26.3°) allowing for the close approach of the solvating benzene molecule to the bridging oxygen atom with a μ‐O···H(benzene) distance of 2.584 Å. Addition of acid HX leads to dissociation of the binuclear μ‐oxodiiron complexes and formation of the mononuclear pentacoordinate FeIII complexes (X)FeMAP and (X)FeDAP (X = AcOH, HCl, etc). Analysis of the kinetic results obtained for the reactions of the μ‐oxodiiron complexes of (aza)porphyrins with acetic acid in benzene solution indicates that the stability of the μ‐oxo bridge towards acid dissociation is primarily determined by its steric accessibility; for species with flexible alkyl chains in β‐pyrrolic positions the stability is much lower than in the presence of shielding meso‐ or β‐phenyl groups.

No abstract

Attempt to obtain imidazoporphyrazine by treatment of formic acid on "diaminoporphyrazine" formed in situ by deselenation of hexaphenyl substituted (1,2,5-selenadiazolo)