Electronic Structure of a Formal Iron(0) Porphyrin Complex Relevant to CO2 Reduction
Open Access
- 5 April 2017
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 56 (8) , 4745-4750
Abstract
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.Keywords
Funding Information
- Max-Planck-Gesellschaft
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