Abstract
Carbon kinetic isotope effects (KIEs) at natural abundances during photolysis of Fe3+-oxalato, malonato, and succinato complexes in aqueous solution were studied to identify the CC bond cleaving mechanism of Fe3+-oxalato complexes under sunlight irradiation. Observed overall KIEs were 5.9‰, 11.5‰, and 8.4‰, respectively. This variation is inconsistent with secondary carbon KIEs for the FeO bond cleavage, but consistent with primary carbon KIEs for sequential cleavage of FeO and CC bonds. Position-specific probability of 13C content estimated KIEs of 5.9‰, 17.2‰, and 17‰ for 12C13C bond cleavage, respectively, indicating the different KIEs for carboxyl-carboxyl and methyl-carboxyl cleavage.
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