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...
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Published in | Journal of the American Chemical Society Vol. 132; no. 11; pp. 3737 - 3750 |
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Main Authors | , , , , , , , |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
24.03.2010
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Subjects | |
Online Access | Get full text |
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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. |
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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 |