N2 activation on a molybdenum–titanium–sulfur cluster

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 N2 has remained challenging, and even the FeMo-cofactor extracted from nitrogenase is not able to reduce N2. Herein, we report the activation of N2 by a metal–sulfur cluster that contains molybdenum and titanium. An N2 moiety bridging two [Mo3S4Ti] cubes is converted into NH3 and N2H4 upon treatment with Brønsted acids in the presence of a reducing agent.
Nitrogenase—whose cofactor consists of a metal–sulfur cluster—catalyzes the production of NH3 from N2, but designing metal–sulfur complexes capable of promoting this conversion remains challenging. Here, the authors report on the activation of N2 by a metal–sulfur cluster containing [Mo3S4Ti] cubes, demonstrating NH3 and N2H4 production.