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Updated: Jul 22, 2025

Light-driven Enzymatic Decarboxylation
Published on: May 22, 2016
Common Photo-oxidative Decarboxylation Mechanism in Iron Hydroxy Carboxylate Complexes
Claresta Joe-Wong1, Richard D Schaller2, Benjamin Gilbert1
1Energy Geoscience Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States.
Abstract:
Photochemical oxidation of dissolved organic matter is a crucial component of carbon cycling in surface waters. Photo-oxidation of iron(III)-carboxylate complexes is of particular interest because complexation with iron(III) can sensitize this functional group to photodecarboxylation. The photo-oxidation mechanism of ferrioxalate has been extensively characterized, but it is unclear whether the mechanism or timing is similar for other more complex carboxylates. In this study, we use time-resolved infrared spectroscopy to demonstrate that Fe(III)-citrate, an aliphatic carboxylate, and Fe(III)-salicylate, an aromatic carboxylate, follow the same photo-oxidation kinetics as ferrioxalate. Hence the data suggest a common mechanism for decarboxylation of iron hydroxy carbonates. Differences in the CO2 yield within 50 ps are qualitatively similar to the long-time-scale quantum yield for Fe(II) production.
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