Electronic Structure of a Formal Iron(0) Porphyrin Complex Relevant to CO2 Reduction

Iron porphyrins can act as potent electrocatalysts for CO2 functionalization. The catalytically active species has been proposed to be a formal Fe(0) porphyrin complex, [Fe­(TPP)]2– (TPP = tetraphenylporphyrin), generated by two-electron reduction of [FeII(TPP)]. Our combined spectroscopic and compu...

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Published in:Inorganic chemistry 2017-04, Vol.56 (8), p.4745-4750
Main Authors: Römelt, Christina, Song, Jinshuai, Tarrago, Maxime, Rees, Julian A, van Gastel, Maurice, Weyhermüller, Thomas, DeBeer, Serena, Bill, Eckhard, Neese, Frank, Ye, Shengfa
Format: Article
Language:English
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Summary:Iron porphyrins can act as potent electrocatalysts for CO2 functionalization. The catalytically active species has been proposed to be a formal Fe(0) porphyrin complex, [Fe­(TPP)]2– (TPP = tetraphenylporphyrin), generated by two-electron reduction of [FeII(TPP)]. Our combined spectroscopic and computational investigations reveal that the reduction is ligand-centered and that [Fe­(TPP)]2– is best formulated as an intermediate-spin Fe­(II) center that is antiferromagnetically coupled to a porphyrin diradical anion, yielding an overall singlet ground state. As such, [Fe­(TPP)]2– contains two readily accessible electrons, setting the stage for CO2 reduction.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.7b00401