Title
Electrochemistry and Spectroelectrochemistry of σ-Bonded Iron(III) Porphyrins with Nonplanar Porphyrin Rings. Reactions of (OETPP)Fe(R) and (OETPP)FeCl, Where R = C6H5, C6F4H, or C6F5 and OETPP Is the Dianion of 2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetraphenylporphyrin
Document Type
Article
Publication Date
5-1-1995
Abstract
A variety of nonplanar σ-bonded phenyl- and (fluorophenyl)iron(III) porphyrins are characterized as to their electrochemical and spectroscopic properties in nonaqueous media. The investigated compounds are represented as (OETPP)Fe(R), where R = C6H5, C6F4H, or C6F5 and OETPP is the dianion of 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin. All three porphyrins contain a low-spin Fe(III) central metal ion and in the case of (OETPP)Fe(C6F5) and (OETPP)Fe(C6F4H) provide the first examples of low-spin iron σ-bonded (fluorophenyl)porphyrins. The site of electron transfer was assigned on the basis of the spectroscopic and electrochemical data for these compounds and by comparison with a related (OETPP)In(C6H5) derivative which was also synthesized and characterized. Comparisons of the results on (OETPP)Fe(R) are also made to data on earlier reported (OEP)Fe(R) derivatives where R = C6H5, C6F4H or C6F5, the latter two of which contain high-spin Fe(III) as compared to the low-spin (OEP)Fe(C6H5) species. (OETPP)Fe(C6H5) undergoes three one-electron oxidations to give a Fe(IV) π dication species. Our results show, for the first time, that the spin state of the iron(III) porphyrin is not a key factor which governs migration of the axial ligand of the electrooxidized species as has previously been proposed. © 1995, American Chemical Society. All rights reserved.
Publication Source (Journal or Book title)
Inorganic Chemistry
First Page
2984
Last Page
2989
Recommended Citation
Radish, K., van Caemelbecke, E., D’Souza, F., Medforth, C., Smith, K., Tabard, A., & Guilard, R. (1995). Electrochemistry and Spectroelectrochemistry of σ-Bonded Iron(III) Porphyrins with Nonplanar Porphyrin Rings. Reactions of (OETPP)Fe(R) and (OETPP)FeCl, Where R = C6H5, C6F4H, or C6F5 and OETPP Is the Dianion of 2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetraphenylporphyrin. Inorganic Chemistry, 34 (11), 2984-2989. https://doi.org/10.1021/ic00115a028