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Ammonia Formation Catalyzed by Dinitrogen-Bridged Dirhenium Complex Bearing PNP-Pincer Ligands under Mild Reaction Conditions

preprint
submitted on 21.04.2020 and posted on 23.04.2020 by Fanqiang Meng, Shogo Kuriyama, Hiromasa Tanaka, Akihito Egi, Kazunari Yoshizawa, Yoshiaki Nishibayashi
A series of rhenium complexes bearing a pyridine-based PNP-type pincer ligand are synthesized from rhenium phosphine complexes as precursors. A dinitrogen-bridged dirhenium complex bearing the PNP-type pincer ligands catalytically converts dinitrogen into ammonia in the reaction with KC8 as a reductant and [HPCy3]BArF4 (Cy = cyclohexyl, ArF = 3,5-(CF3)2C6H3) as a proton source at –78 °C to afford 8.4 equiv of ammonia based on the rhenium atom of the catalyst. The rhenium-dinitrogen complex also catalyzes silylation of dinitrogen in the reaction with KC8 as a reductant and Me3SiCl as a silylating reagent under ambient reaction conditions to afford 11.3 equiv of tris(trimethylsilyl)amine based on the rhenium atom of the catalyst. These results demonstrate the first successful example of catalytic nitrogen fixation under mild reaction conditions by using rhenium-dinitrogen complexes as catalysts.

History

Email Address of Submitting Author

ynishiba@sys.t.u-tokyo.ac.jp

Institution

The University of Tokyo

Country

JAPAN

ORCID For Submitting Author

0000-0001-9739-9588

Declaration of Conflict of Interest

no conflict of interest

Version Notes

version 01

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