Relative Axial Ligand Orientation in Bis(imidazole)iron(II) Porphyrinates: Are “Picket Fence” Derivatives Different?

Author:

Li Jianfeng1,Nair Smitha M.1,Noll Bruce C.1,Schulz Charles E.1,Scheidt W. Robert1

Affiliation:

1. Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, and Department of Physics, Knox College, Galesburg, Illinois 61401

Publisher

American Chemical Society (ACS)

Subject

Inorganic Chemistry,Physical and Theoretical Chemistry

Reference71 articles.

1. Models of the Bis-Histidine-Ligated Electron-Transferring Cytochromes. Comparative Geometric and Electronic Structure of Low-Spin Ferro- and Ferrihemes

2. The following abbreviations are used in this paper: Porph, a generalized porphyrin dianion; TMP, dianion of meso-tetramesitylporphyrin; TPP, dianion of meso-tetraphenylporphyrin; TTP, dianion of meso-tetratolylporphyrin, TpivPP, dianion of α,α,α,α-tetrakis(o-pivalamidophenyl)porphyrin; TF5PPBr8, dianion of 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin; HIm, imidazole; 1-MeIm, 1-methylimidazole; 2-MeHIm, 2-methylimidazole; 4-MeHIm, 4-methylimidazole; 1,2-Me2Im, 1,2-dimethylimidazole; 1-AcIm, 1-acetylimidazole; 1-SiMe3Im, 1-(trimethylsilyl)imidazole; 1-VinylIm, 1-vinylimidazole; 1-BzylIm, 1-benzylimidazole; RIm, generalized imidazole;Py, pyridine; 3-ClPy, 3-chloropyridine; 4-CNPy, 4-cyanopyridine; 3-CNPy, 3-cyanopyridine; 4-MePy, 4-methylpyridine; 4-NMe2Py, 4-(dimethylamino)pyridine; Pip, piperidine; Pyz, pyrazine; Im −, imidazolate; 2-MeIm−, 2-methylimidazolate; Np, porphyrinato nitrogen; Nax, nitrogen of axial ligands; Nim, nitrogen of imidazole ligands; EPR, electron paramagnetic resonance.

3. Molecular stereochemistry and crystal structure of a ‘spin-equilibrium’(S= 1/2, S= 5/2) haemichrome salt: bis-(3-chloropyridine)octaethylporphinatoiron(III) perchlorate

4. Structural characterization of a variable-spin(porphinato)iron(III) complex. Molecular stereochemistry of bis(3-chloropyridine)(octaethylporphinato)iron(III) perchlorate at 98 K (S = 1/2) and 293 K (S = 1/2, S = 5/2)

5. Control of spin state in (porphinato)iron(III) complexes. An axial ligand orientation effect leading to an intermediate-spin complex. Molecular structure and physical characterization of the monoclinic form of bis(3-chloropyridine)(octaethylporphinato)iron(III) perchlorate

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