European Journal of Inorganic Chemistry 2018-03-25

Insight into Solvent Coordination of an Iron Porphyrin Hydroxylamine Complex from Spectroscopy and DFT Calculations

Md. Hafizur Rahman; Michael D. Ryan

Index: 10.1002/ejic.201800040

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Abstract

The reduction of Fe(OEP)(NO) in the presence of substituted phenols leads to a three‐electron reduction to form Fe(OEP)(NH2OH), which has been characterized by visible spectroscopy and electron stoichiometry. In this work, we have further characterized this species using infrared and 1H NMR spectroscopy, along with DFT calculations. The infrared bands in the 3400–3600 cm–1 region, due to hydroxylamine, were significantly downshifted to the 2500–2700 cm–1 region when 4‐[D1]chlorophenol replaced the normal abundance acid. Using 1H NMR spectroscopy, the hydroxylamine and the meso‐protons were identified. From DFT calculations, the 1H NMR spectra were most consistent with a six‐coordinate complex, Fe(OEP)(NH2OH)(THF).

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