Unknown

Dataset Information

0

Relative axial ligand orientation in bis(imidazole)iron(II) porphyrinates: are "picket fence" derivatives different?


ABSTRACT: The synthesis of three new bis(imidazole)-ligated iron(II) picket fence porphyrin derivatives, [Fe(TpivPP)(1-RIm) 2] 1-RIm = 1-methyl-, 1-ethyl-, or 1-vinylimidazole) are reported. X-ray structure determinations reveal that the steric requirements of the four alpha,alpha,alpha,alpha-o-pivalamidophenyl groups lead to very restricted rotation of the imidazole ligand on the picket side of the porphyrin plane; the crowding leads to an imidazole plane orientation eclipsing an iron-porphyrin nitrogen bond. An unusual feature for these diamagnetic iron(II) species is that all three derivatives have the two axial ligands with a relative perpendicular orientation; the dihedral angles between the two imidazole planes are 77.2 degrees , 62.4 degrees , and 78.5 degrees . All three derivatives have nearly planar porphyrin cores. Mössbauer spectroscopic characterization shows that all three derivatives have quadrupole splitting constants around 1.00 mm/s at 100K.

SUBMITTER: Li J 

PROVIDER: S-EPMC2543116 | biostudies-literature | 2008 May

REPOSITORIES: biostudies-literature

altmetric image

Publications

Relative axial ligand orientation in bis(imidazole)iron(II) porphyrinates: are "picket fence" derivatives different?

Li Jianfeng J   Nair Smitha M SM   Noll Bruce C BC   Schulz Charles E CE   Scheidt W Robert WR  

Inorganic chemistry 20080320 9


The synthesis of three new bis(imidazole)-ligated iron(II) picket fence porphyrin derivatives, [Fe(TpivPP)(1-RIm) 2] 1-RIm = 1-methyl-, 1-ethyl-, or 1-vinylimidazole) are reported. X-ray structure determinations reveal that the steric requirements of the four alpha,alpha,alpha,alpha-o-pivalamidophenyl groups lead to very restricted rotation of the imidazole ligand on the picket side of the porphyrin plane; the crowding leads to an imidazole plane orientation eclipsing an iron-porphyrin nitrogen  ...[more]

Similar Datasets

| S-EPMC3384769 | biostudies-literature
| S-EPMC3827975 | biostudies-literature
| S-EPMC6103255 | biostudies-literature
| S-EPMC8048935 | biostudies-literature
| S-EPMC9231596 | biostudies-literature
| S-EPMC7421780 | biostudies-literature
| S-EPMC3614349 | biostudies-literature
| S-EPMC7037510 | biostudies-literature
| S-EPMC3273671 | biostudies-literature
| S-EPMC3613136 | biostudies-literature