Issue 30, 2015

Synthesis and characterization of a modified “picket fence” porphyrin complex – stronger π bonding interactions between Fe(ii) and axial ligands

Abstract

A new, modified “picket fence” porphyrin is synthesized and its bis(imidazole)-ligated iron(II) derivative [Fe(MbenTpivPP)(1-MeIm)2] is investigated. X-ray structure determinations demonstrate that [Fe(MbenTpivPP)(1-MeIm)2] has structural features of a near planar porphyrin plane, a relative perpendicular ligand orientation, and one unusually large absolute ligand orientation (φ). The combination of these features leads to a new type of species that is different from previously reported analogues. Further structural examination reveals a strong correlation between the mutual ligand orientations (θ) and the axial Fe–NIm bond distances, which is detailed for the first time. Mössbauer spectroscopic characterization shows that the low spin derivative has a quadrupole splitting of 0.99 mm s−1 at 100 K.

Graphical abstract: Synthesis and characterization of a modified “picket fence” porphyrin complex – stronger π bonding interactions between Fe(ii) and axial ligands

Supplementary files

Article information

Article type
Paper
Submitted
09 Mar 2015
Accepted
22 Jun 2015
First published
24 Jun 2015

Dalton Trans., 2015,44, 13651-13661

Author version available

Synthesis and characterization of a modified “picket fence” porphyrin complex – stronger π bonding interactions between Fe(II) and axial ligands

B. He, C. E. Schulz and J. Li, Dalton Trans., 2015, 44, 13651 DOI: 10.1039/C5DT00941C

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