Preparation of Non-heme {FeNO}<sup>7</sup> Models
of Cysteine Dioxygenase: Sulfur versus Nitrogen Ligation and Photorelease
of Nitric Oxide
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Abstract
We
present the synthesis and spectroscopic characterization of
[Fe(NO)(N3PyS)]BF<sub>4</sub> (<b>3</b>), the first structural
and electronic model of NO-bound cysteine dioxygenase. The nearly
isostructural all-N-donor analogue [Fe(NO)(N4Py)](BF<sub>4</sub>)<sub>2</sub> (<b>4</b>) was also prepared, and comparisons of <b>3</b> and <b>4</b> provide insight regarding the influence
of S vs N ligation in {FeNO}<sup>7</sup> species. One key difference
occurs upon photoirradiation, which causes the fully reversible release
of NO from <b>3</b>, but not from <b>4</b>