Just a Proton: Distinguishing the Two Electronic States of Five-Coordinate High-Spin Iron(II) Porphyrinates with Imidazole/ate Coordination

We report detailed studies on two S = 2 electronic states of high-spin iron(II) porphyrinates. These two states are exemplified by the five-coordinate derivatives with either neutral imidazole or anionic imidazolate as the axial ligand. The application of several physical methods all demonstrate dis...

Full description

Saved in:
Bibliographic Details
Published inJournal of the American Chemical Society Vol. 132; no. 11; pp. 3737 - 3750
Main Authors Hu, Chuanjiang, Sulok, Corinne D, Paulat, Florian, Lehnert, Nicolai, Twigg, Anna I, Hendrich, Michael P, Schulz, Charles E, Scheidt, W. Robert
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 24.03.2010
Subjects
Circular Dichroism
Crystallography, X-Ray
Electron Spin Resonance Spectroscopy
Electrons
Imidazoles - chemistry
Iron - chemistry
Magnetics
Metalloporphyrins - chemistry
Models, Molecular
Molecular Conformation
Protons
Quantum Theory
Spectroscopy, Mossbauer
Online AccessGet full text

Cover

More Information
Summary:We report detailed studies on two S = 2 electronic states of high-spin iron(II) porphyrinates. These two states are exemplified by the five-coordinate derivatives with either neutral imidazole or anionic imidazolate as the axial ligand. The application of several physical methods all demonstrate distinctive differences between the two states. These include characteristic molecular structure differences, Mössbauer spectra, magnetic circular dichroism spectroscopy, and integer-spin EPR spectral distinctions. These distinctions are supported by DFT calculations. The two states are characterized by very different spatial properties of the doubly occupied orbital of the high-spin that are consonant with the physical properties.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
University of Michigan
Carnegie Mellon University
Knox College
Present address: College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 China
University of Notre Dame
ISSN:0002-7863
1520-5126
DOI:10.1021/ja907584x