Preparation of Non-heme {FeNO}<sup>7</sup> Models of Cysteine Dioxygenase: Sulfur versus Nitrogen Ligation and Photorelease of Nitric Oxide

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>

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