Catalytic transfer hydrogenation of N<sub>2</sub> to NH<sub>3</sub> via a photoredox catalysis strategy.

Johansen, Christian M; Boyd, Emily A; Peters, Jonas C · Sci Adv · 2022

basic_science · Level V

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Abstract

Inspired by momentum in applications of reductive photoredox catalysis to organic synthesis, photodriven transfer hydrogenations toward deep (>2 e<sup>-</sup>) reductions of small molecules are attractive compared to using harsh chemical reagents. Noteworthy in this context is the nitrogen reduction reaction (N<sub>2</sub>RR), where a synthetic photocatalyst system had yet to be developed. Noting that a reduced Hantzsch ester (HEH<sub>2</sub>) and related organic structures can behave as 2 e<sup>-</sup>/2 H<sup>+</sup> photoreductants, we show here that, when partnered with a suitable catalyst (Mo) under blue light irradiation, HEH<sub>2</sub> facilitates delivery of successive H<sub>2</sub> equivalents for the 6 e<sup>-</sup>/6 H<sup>+</sup> catalytic reduction of N<sub>2</sub> to NH<sub>3</sub>; this catalysis is enhanced by addition of a photoredox catalyst (Ir). Reductions of additional substrates (nitrate and acetylene) are also described.