N<sub>2</sub> activation on a molybdenum-titanium-sulfur cluster.

Ohki, Yasuhiro; Uchida, Keisuke; Tada, Mizuki; Cramer, Roger E; Ogura, Takashi; Ohta, Takehiro · Nat Commun · 2018

basic_science · Level V

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Abstract

The FeMo-cofactor of nitrogenase, a metal-sulfur cluster that contains eight transition metals, promotes the conversion of dinitrogen into ammonia when stored in the protein. Although various metal-sulfur clusters have been synthesized over the past decades, their use in the activation of N<sub>2</sub> has remained challenging, and even the FeMo-cofactor extracted from nitrogenase is not able to reduce N<sub>2</sub>. Herein, we report the activation of N<sub>2</sub> by a metal-sulfur cluster that contains molybdenum and titanium. An N<sub>2</sub> moiety bridging two [Mo<sub>3</sub>S<sub>4</sub>Ti] cubes is converted into NH<sub>3</sub> and N<sub>2</sub>H<sub>4</sub> upon treatment with Brønsted acids in the presence of a reducing agent.