Unexpected nitrosyl-group bending in six-coordinate [M(NO)](6) sigma-bonded aryl(iron) and -(ruthenium) porphyrins.

The six-coordinate nitrosyl sigma-bonded aryl(iron) and -(ruthenium) porphyrin complexes (OEP)Fe(NO)(p-C(6)H(4)F) and (OEP)Ru(NO)(p-C(6)H(4)F) (OEP = octaethylporphyrinato dianion) have been synthesized and characterized. Single-crystal X-ray structure determinations reveal an unprecedented bending and tilting of the MNO group for both [MNO](6) species as well as significant lengthening of trans axial bond distances. In (OEP)Fe(NO)(p-C(6)H(4)F) the Fe-N-O angle is 157.4(2) degrees, the nitrosyl nitrogen atom is tilted off of the normal to the heme plane by 9.2 degrees, Fe-N(NO) = 1.728(2) A, and Fe-C(aryl) = 2.040(3) A. In (OEP)Ru(NO)(p-C(6)H(4)F) the Ru-N-O angle is 154.9(3) degrees, the nitrosyl nitrogen atom is tilted off of the heme normal by 10.8 degrees, Ru-N(NO) = 1.807(3) A, and Ru-C(aryl) = 2.111(3) A. We show that these structural features are intrinsic to the molecules and are imposed by the strongly sigma-donating aryl ligand trans to the nitrosyl. Density functional-based calculations reproduce the structural distortions observed in the parent (OEP)Fe(NO)(p-C(6)H(4)F) and, combined with the results of extended Hückel calculations, show that the observed bending and tilting of the FeNO group indeed represent a low-energy conformation. We have identified specific orbital interactions that favor the unexpected bending and tilting of the FeNO group. The aryl ligand also affects the Fe-NO pi-bonding as measured by infrared and (57)Fe Mössbauer spectroscopies. The solid-state nitrosyl stretching frequencies for the iron complex (1791 cm(-)(1)) and the ruthenium complex (1773 cm(-)(1)) are significantly reduced compared to their respective [MNO](6) counterparts. The Mössbauer data for (OEP)Fe(NO)(p-C(6)H(4)F) yield the quadrupole splitting parameter +0.57 mm/s and the isomer shift 0.14 mm/s at 4.2 K. The results of our study show, for the first time, that bent Fe-N-O linkages are possible in formally ferric nitrosyl porphyrins.

Molecular structure of an Fe(IV) species:.

The molecular structure of the formal iron(IV) porphyrinate derivative, [[Fe(TTP)]2N]SbCl6 (TTP = tetratolylporphyrinate), is reported. The structural parameters are compared to the previously reported species [Fe(TPP)]2N, in which the iron oxidation state is +3.5. Both the equatorial and axial bond distances in [[Fe(TTP)]2N]SbCl6 are slightly shortened and consistent with an increased formal charge on iron. The value for the axial Fe-N distance is 1.6280(7) A, and the average value of the equatorial Fe-Np distances is 1.979(5) A. The Mössbauer isomer shift decreases upon oxidation, again consistent with an increase in formal charge. Values for the isomer shift at room temperature are -0.13 mm/s for [[Fe(TTP)]2N]SbCl6 and 0.04 mm/s for [Fe(TTP)]2N. Crystal data for [[Fe(TTP)]2N]SbCl6 are as follows: orthorhombic, space group Fddd, Z = 8, a = 23.689(2) A, b = 31.056(3) A, c = 22.7788(18) A.

Structural and electronic characterization of nitrosyl(octaethylporphinato)iron(III) perchlorate derivatives.

The synthesis and crystallographic characterization of the five-coordinate iron(III) porphyrinate complex [Fe(OEP)(NO)]ClO4 are reported. This [FeNO]6 complex has a nearly linear Fe-N-O group (angle = 173.19(13) degrees) with a small off-axis tilt of the Fe-N(NO) vector from the heme normal (angle = 4.6 degrees); the Fe-N(NO) distance is 1.6528(13) A and the iron is displaced 0.32 A out-of-plane. The complex forms a tight cofacial pi-pi dimer in the solid state. Mössbauer spectra for this derivative as well as for a related crystalline form are measured both in zero applied magnetic field and in a 7 T applied field. Fits to the measurements made in applied magnetic field demonstrate that both crystalline forms of [Fe(OEP)(NO)]ClO4 have a diamagnetic ground state at 4.2 K. The observed isomer shifts (delta = 0.22-0.24 mm/s) are smaller than those typically observed for low-spin iron(III) porphyrinates. Analogous Mössbauer measurements are also obtained for a six-coordinate derivative, [Fe(OEP)(Iz)(NO)]ClO4 (Iz = indazole). The observed isomer shift for this species is smaller still (delta = 0.02 mm/s). All derivatives show a strong temperature dependence of the isomer shift. The data emphasize the strongly covalent nature of the FeNO group. The Mössbauer isomer shifts suggest formal oxidation states greater than +3 for iron, but the NO stretching frequencies are not consistent with such a large charge transfer to NO. Differences in the observed nitrosyl stretching frequencies of the two crystalline forms of [Fe(OEP)(NO)]ClO4 are discussed.

Magnetic interactions in the high-spin iron(III) oxooctaethylchlorinato derivative [Fe(oxoOEC)(Cl)] and its pi-cation radical [Fe(oxoOEC.)(Cl)]SbCl6.

The preparation and characterization of the beta-oxochlorin derivative [3,3,7,8,12,13,17,18-octaethyl-(3H)-porphin-2-onato(2-)]iron(III) chloride, [Fe(oxoOEC)(Cl)], and its pi-cation radical derivative [Fe(oxoOEC.)(Cl)]SbCl6 is described. Both compounds have been characterized by single-crystal X-ray structure determinations, IR, UV/vis/near-IR, and Mössbauer spectroscopies, and temperature-dependent magnetic susceptibility measurements. The macrocycles of [Fe(oxoOEC)(Cl)] and [Fe(oxoOEC.)(Cl)]SbCl6 are both saddled, and [Fe(oxoOEC.)(Cl)]-SbCl6 is slightly ruffled as well. [Fe(oxoOEC)(Cl)] shows a laterally shifted dimeric unit in the solid state, with a mean plane separation of 3.39 A and a lateral shift of 7.39 A. Crystal data for [Fe(oxoOEC)(Cl)]: triclinic, space group P1, Z = 2, a = 9.174(2) A, b = 13.522(3) A, c = 14.838(3) A, alpha = 95.79(3) degrees, beta = 101.46(2) degrees, gamma = 104.84(3) degrees. Upon oxidation, the inter-ring geometric parameters increase; the mean plane separation and the lateral shift of the dimeric unit of [Fe(oxoOEC.)(Cl)]SbCl6 are 4.82 and 8.79 A, respectively. Crystal data for [Fe(oxoOEC.)(Cl)]SbCl6: monoclinic, space group Cc, Z = 4, a = 19.8419(13) A, b = 10.027(2) A, c = 22.417(4) A, beta = 96.13(2) degrees. A broad near-IR absorption band appears at 1415 nm for the pi-cation radical, [Fe(oxoOEC.)(Cl)]SbCl6. Zero-field Mössbauer measurements at 4.2 K for both [Fe(oxoOEC)(Cl)] and [Fe(oxoOEC.)(Cl)]SbCl6 confirmed that the oxidation state of the iron atom did not change upon chemical oxidation. Solid-state magnetic susceptibility measurements for [Fe(oxoOEC.)(Cl)]SbCl6 resulted in a large temperature dependence of the magnetic moment that can best be fit with a model that includes a zero-field splitting parameter of D = 6 cm-1, antiferromagnetic intermolecular iron-iron coupling (2JFe-Fe = -0.14 cm-1), antiferromagnetic intramolecular iron-radical coupling (2JFe-r = -76 cm-1), and antiferromagnetic radical-radical coupling (2Jr-r = -13 cm-1).

Mössbauer and electron paramagnetic resonance studies of chloroperoxidase following mechanism-based inactivation with allylbenzene.

We have used Mössbauer and electron paramagnetic resonance (EPR) spectroscopy to study a heme-N-alkylated derivative of chloroperoxidase (CPO) prepared by mechanism-based inactivation with allylbenzene and hydrogen peroxide. The freshly prepared inactivated enzyme ("green CPO") displayed a nearly pure low-spin ferric EPR signal with g = 1.94, 2.15, 2.31. The Mössbauer spectrum of the same species recorded at 4.2 K showed magnetic hyperfine splittings, which could be simulated in terms of a spin Hamiltonian with a complete set of hyperfine parameters in the slow spin fluctuation limit. The EPR spectrum of green CPO was simulated using a three-term crystal field model including g-strain. The best-fit parameters implied a very strong octahedral field in which the three 2T2 levels of the (3d)5 configuration in green CPO were lowest in energy, followed by a quartet. In native CPO, the 6A1 states follow the 2T2 ground state doublet. The alkene-mediated inactivation of CPO is spontaneously reversible. Warming of a sample of green CPO to 22 degrees C for increasing times before freezing revealed slow conversion of the novel EPR species to two further spin S = 1/2 ferric species. One of these species displayed g = 1.82, 2.25, 2.60 indistinguishable from native CPO. By subtracting spectral components due to native and green CPO, a third species with g = 1.86, 2.24, 2.50 could be generated. The EPR spectrum of this "quasi-native CPO," which appears at intermediate times during the reactivation, was simulated using best-fit parameters similar to those used for native CPO.

Mössbauer and electron paramagnetic resonance studies of horseradish peroxidase and its catalytic intermediates.

We report Mössbauer and EPR measurements on horseradish peroxidase in the native state and the reaction intermediates with peroxide and chlorite. A detailed analysis of the electronic state of the heme iron is given, and comparisons are drawn with related systems. The native enzyme is high-spin ferric and thus has three Kramers doublets. The unusual magnetic properties of the ground doublet and the large energy of the second, (E2-E1)/k approximately equal to 41 K, and third doublet, (E3-E1)/k greater than or equal to 170 K, can be modeled with a quartet admixture of approximately 11% to the spin sextet. All evidence suggests a ferryl, OFeIV, state of the heme iron in compounds I and II and related complexes. The small isomer shift, delta Fe approximately equal to 0.06 mm/s, the (positive) quadrupole splitting, delta EQ approximately equal to 1.4 mm/s, the spin S = 1, and the large positive zero field splitting, D/k approximately equal to 35 K, are all characteristic of the ferryl state. In the green compound I the iron weakly couples to a porphyrin radical with spin S' = 1/2. A phenomenological model with a weak exchange interaction S . J . S', magnitude of less than or equal to 0.1 D, reproduces all Mössbauer and EPR data of compound I, but the structural origin of the exchange and its apparent distribution require further study. Reaction of horseradish peroxidase with chlorite leads to compound X with delta Fe = 0.07 mm/s and delta EQ = 1.53 mm/s, values that are closest to those of compound II. The diamagnetism of compound III and its Mössbauer parameters delta Fe = 0.23 mm/s and delta EQ = -2.31 mm/s at 4.2 K clearly identify it as an oxyheme adduct.

[Viscosity of blood and sensorineural hearing loss (author's transl)]. / Blutviskosität und Innenohrschwerhörigkeit

A statistical survey about the results of treatment of Pentoxifyllin (Trental) in acute and long-standing sensorineural hearing losses is given. The pharmacological effect of viscosity lowering in such patients is demonstrated. The role of erythrocytes and their behaviour in relation to the viscosity of blood its showed by means of literature.

[Therapeutical results of non-acute perceptive hearing loss with vasoactive medicaments (author's transl)]. / Ergebnisse der Therapie nichtakuter Schallempfindungs-schwerhörigkeit mit vasoaktiven Medikamenten

67 patients who are suffering from a non-acute perceptive hearing loss were treted by several vasoactive medicaments. Besides pharmacological aspects of derivatives of di-ethyl-amino-ethyl-alcohol and of xanthine were discussed. The therapeutical results were subjected to comparing views.