Unknown

Dataset Information

0

Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex.


ABSTRACT: O2 bubbling into a THF solution of Fe(II)(BDPP) (1) at -80 °C generates a reversible bright yellow adduct 2. Characterization by resonance Raman and Mössbauer spectroscopy provides complementary insights into the nature of 2. The former shows a resonance-enhanced vibration at 1125 cm(-1), which can be assigned to the ν(O-O) of a bound superoxide, while the latter reveals the presence of a high-spin iron(III) center that is exchange-coupled to the superoxo ligand, like the Fe(III)-O2(-) pair found for the O2 adduct of 4-nitrocatechol-bound homoprotocatechuate 2,3-dioxygenase. Lastly, 2 oxidizes dihydroanthracene to anthracene, supporting the notion that Fe(III)-O2(-) species can carry out H atom abstraction from a C-H bond to initiate the 4-electron oxidation of substrates proposed for some nonheme iron enzymes.

SUBMITTER: Chiang CW 

PROVIDER: S-EPMC4132977 | biostudies-literature |

REPOSITORIES: biostudies-literature

Similar Datasets

| S-EPMC2864595 | biostudies-literature
| S-EPMC2947897 | biostudies-literature
| S-EPMC5843466 | biostudies-literature
| S-EPMC4838200 | biostudies-literature
| S-EPMC6047074 | biostudies-literature
| S-EPMC7909310 | biostudies-literature
| S-EPMC5711427 | biostudies-literature
| S-EPMC4241270 | biostudies-literature
| S-EPMC6201693 | biostudies-literature
| S-EPMC6556537 | biostudies-literature