Cyanide Complexes of Iron Corrolates:  Spin Delocalization and Autoreduction

Complex formation of (7,13-dimethyl-2,3,8,12,17,18-hexaethylcorrolato)iron chloride, [(7,13-Me2Et6C)FeCl], with cyanide ion in dimethylformamide, DMF-d 7, was studied by 1H NMR spectroscopy. It is found that a bis-cyanide complex is formed initially, in which the electron configuration is a low-spin...

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Bibliographic Details
Published in:Inorganic chemistry 2001-11, Vol.40 (23), p.5795-5798
Main Authors: Cai, Sheng, Licoccia, Silvia, Walker, F. Ann
Format: Article
Language:English
Subjects:
Cations
Chemical Phenomena
Chemistry, Physical
Cyanides - chemistry
Electron Spin Resonance Spectroscopy
Ferrous Compounds - chemistry
Iron - chemistry
Magnetic Resonance Spectroscopy
Metalloporphyrins - chemistry
Molecular Structure
Oxidation-Reduction
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Summary:Complex formation of (7,13-dimethyl-2,3,8,12,17,18-hexaethylcorrolato)iron chloride, [(7,13-Me2Et6C)FeCl], with cyanide ion in dimethylformamide, DMF-d 7, was studied by 1H NMR spectroscopy. It is found that a bis-cyanide complex is formed initially, in which the electron configuration is a low-spin Fe(III) corrolate(2−•). This complex is not stable, and it is readily reduced with an excess of cyanide in the solution. The reduction occurs at the corrole ring instead of on the iron center giving the monocyanide complex of the low-spin Fe(III) corrole, [(7,13-Me2Et6C)FeCN]-. Thus, this is a case where an axial ligand serves as a reducing agent of the macrocycle and not of the metal.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic010312i