Leu-M

Prediction of molecular properties and molecular spectroscopy with density functional theory: From fundamental theory to exchange-coupling

Surface chemistry of porphyrins and phthalocyanines

Mechanistic aspects of the reactions of nitric oxide with transition-metal complexes.

Trans-effects in octahedral transition metal complexes

The Synthetic and Structural Chemistry of Heme Derivatives with Nitric Oxide Ligands

The reaction of the iron(II) picket fence porphyrin derivative [Fe(TpivPP)(NO2)]- (Nasri et al. J. Am. Chem. Soc. 1991, 113, 717) with NO has been examined. The result is a new hexacoordinated iron...

Sharing the π-Bonding. An Iron Porphyrin Derivative with Trans, π-Accepting Axial Ligands. Synthesis, EPR and Mössbauer Spectra, and Molecular Structure of Two Forms of the Complex Nitronitrosyl(α,α,α,α-tetrakis(o-pivalamidophenyl)- porphinato)ferrate(II)

The six-coordinate nitrosyl σ-bonded aryl(iron) and -(ruthenium) porphyrin complexes (OEP)Fe(NO)(p-C6H4F) and (OEP)Ru(NO)(p-C6H4F) (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-C6H4F) the Fe−N−O angle is 157.4(2)°, the nitrosyl nitrogen atom is tilted off of the normal to the heme plane by 9.2°, Fe−N(NO) = 1.728(2) A, and Fe−C(aryl) = 2.040(3) A. In (OEP)Ru(NO)(p-C6H4F) the Ru−N−O angle is 154.9(3)°, the nitrosyl nitrogen atom is tilted off of the heme normal by 10.8°, 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 σ-donating aryl ligand trans to the nitrosyl. Density functional-based calculations reproduce the structural distortions observed in the parent (...

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

The preparation and molecular structures of several five-coordinate (nitrosyl)iron(II) porphyrinate derivatives are described. The derivatives reported include two crystalline forms of [Fe(OEP)(NO)] (OEP = 2,3,7,8,12,13,17,18-octaethylporphyrin dianion), three conformationally distinct forms of [Fe(TPPBr4)(NO)] (TPPBr4 = 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrin dianion), and [Fe(oxoOEC)(NO)] (oxoOEC = 3,3,7,8,12,13,17,18-octaethyl-3H-porphin-2-onato(2-) dianion). These complexes differ in the nature and position of the β-pyrrolic and meso substituents, and in the conformation adopted by the porphyrinato cores in the crystalline state. For one form of [Fe(OEP)(NO)], the structure was determined at three temperatures (130(2), 213(2), and 293(2) K). For two of the structures the X-ray data were collected to exceedingly high resolution. For each structure, we observed a bent FeNO group (Fe−N−O angles ranging from 142.74(8)° to 147.9(8)°) and a significant off-axis tilt of the nitrosyl group irresp...

Intrinsic Structural Distortions in Five-Coordinate (Nitrosyl)iron(II) Porphyrinate Derivatives

The high-resolution crystal structure for [Co(OEP)(NO)] shows that the axial Co−N(NO) vector is tilted from the normal to the porphyrin plane. The off-axis tilt is correlated with an asymmetry in the equatorial Co−Np bond distances.

Mary K. Ellison

Papers

The Synthetic and Structural Chemistry of Heme Derivatives with Nitric Oxide Ligands

Sharing the π-Bonding. An Iron Porphyrin Derivative with Trans, π-Accepting Axial Ligands. Synthesis, EPR and Mössbauer Spectra, and Molecular Structure of Two Forms of the Complex Nitronitrosyl(α,α,α,α-tetrakis(o-pivalamidophenyl)- porphinato)ferrate(II)

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

Intrinsic Structural Distortions in Five-Coordinate (Nitrosyl)iron(II) Porphyrinate Derivatives

Tilt/Asymmetry in Nitrosyl Metalloporphyrin Complexes: The Cobalt Case.