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.

Single-crystal EPR measurements have been performed on the triclinic form of [Fe(OEP)(NO)] (Ellison, M. K.; Scheidt, W. R. J. Am. Chem. Soc. 1997, 119, 7404) and on the isomorphous cobalt derivative [Co(OEP)(NO)] (Ellison, M. K.; Scheidt, W. R. Inorg. Chem. 1998, 37, 382) which has been doped with [Fe(OEP)(NO)]. Principal values of the g tensor determined at room temperature are gmax = 2.106, gmid = 2.057, and gmin = 2.015. The principal direction associated with the minimum g value lies 8 degrees from the Fe-N(NO) direction, 2 degrees from the normal to the heme plane, and 42 degrees from the N-O direction. The direction associated with the maximum g value lies 9 degrees from the normal to the Fe-N-O plane. The fact that the direction of gmin is near the Fe-N(NO) direction is consistent with the dominant role of spin-orbit coupling at the iron atom in determining the g tensor and with the picture of the electronic structure of the compound from restricted calculations, which makes the half-filled orbital mostly dz2 on the iron atom. The hyperfine tensor is nearly isotropic and was only resolved in the doped samples. Principal values of the A tensor determined at room temperature are 40.9, 49.7, and 42.7 MHz. Principal values of the g tensor determined from the doped samples at 77 K are gmax = 2.110, gmid = 2.040, and gmin = 2.012. Principal values of the A tensor are 42.5, 52.8, and 44.1 MHz at 77 K. The small change in g values with temperature is in contrast to the large temperature dependence on g values observed in samples of MbNO (Hori et al. J. Biol. Chem. 1981, 256, 7849).

Nuclear resonance vibrational spectra have been obtained for six five-coordinate imidazole-ligated iron(II) porphyrinates, [Fe(Por)(L)] (Por = tetraphenylporphyrinate, octaethylporphyrinate, tetratolylporphyrinate or protoporphyrinate IX and L = 2-methylimidazole or 1,2-dimethylimidazole). Measurements have been made on both powder and oriented crystal samples. The spectra are dominated by strong signals around 200–300 cm−1. Although the in-plane and out-of-plane vibrations are seriously overlapped, oriented crystal spectra allow their deconvolution. Thus, oriented crystal experimental data, along with DFT calculations, enable the assignment of key vibrations in the spectra. Molecular dynamics are also discussed. The nature of the Fe–NIm vibrations has been elaborated further than was possible from resonance Raman studies. Our study suggests that the Fe motions are coupled with the porphyrin core and peripheral groups motions. Both peripheral groups and their conformations have significant influence on the vibrational spectra (position and shape).

The complex anion bis(azido)(tetraphenylporphinato)ferrate(III) has been synthesized and characterized by variable-temperature X-ray structure determinations, powder and single-crystal EPR, IR, and Mössbauer spectroscopy, and magnetic susceptibility measurements. The synthesis utilizes 18-crown-6 to solubilize sodium azide in the synthetic procedure. All physical data for [Na(18C6)(H(2)O)(2)][Fe(TPP)(N(3))(2)].2C(6)H(5)Cl are consistent with a thermal spin-equilibrium system: low spin (S = (1)/(2)) right harpoon over left harpoon high spin (S = (5)/(2)). Structure determinations at 130 and 293 K show equatorial and axial Fe-N bond elongation at 293 K. Fe-N(p) = 1.9991(11) Å, Fe-N(az) = 1.9734(14) Å at 130 K, and Fe-N(p) = 2.010(4) Å, Fe-N(az) = 1.998(2) Å at 293 K. The EPR g values for a powder sample at 4.2 K are 1.81, 2.18, and 2.70. A fit of the powder EPR spectrum at 4.2 K with a crystal field model that allows quartet and sextet admixtures suggests that the first sextet state is approximately 655 cm(-)(1) above the ground doublet. Single-crystal EPR data indicate that the largest g value occurs at an angle of 56 degrees from the porphyrin normal and at 35 and 81 degrees from the Fe-N(p) vectors. The asymmetric azide IR absorption bands at 2014 and 2036 cm(-)(1) can be assigned to low- and high-spin species, respectively, and display temperature-dependent intensities. The Mössbauer experiments reveal a gradual decrease in the quadrupole splitting as the temperature increases from 140 to 300 K. The magnetic susceptibility measurements show a gradual increase of &mgr;(eff) with temperature. Crystal data for [Na(18C6)(H(2)O)(2)][Fe(TPP)(N(3))(2)].2C(6)H(5)Cl (130 K): a = 11.417(2) Å, b = 12.371(4) Å, c = 12.628(2) Å, alpha = 64.30(2) degrees, beta = 77.18(3) degrees, gamma = 77.67(2) degrees, triclinic, space group P&onemacr;, Z = 1. Crystal data (293 K): a = 11.7652(12) Å, b = 12.6488(6) Å, c = 12.8608(13) Å, alpha = 62.02(2) degrees, beta = 75.996(7) degrees, gamma = 75.465(9) degrees.