Metallacyclic actinide catalysts for dinitrogen conversion to ammonia and secondary amines

Nat Chem. 2020 Jul;12(7):654-659. doi: 10.1038/s41557-020-0457-9. Epub 2020 May 4.

Abstract

Chemists have spent over a hundred years trying to make ambient temperature/pressure catalytic systems that can convert atmospheric dinitrogen into ammonia or directly into amines. A handful of successful d-block metal catalysts have been developed in recent years, but even binding of dinitrogen to an f-block metal cation is extremely rare. Here we report f-block complexes that can catalyse the reduction and functionalization of molecular dinitrogen, including the catalytic conversion of molecular dinitrogen to a secondary silylamine. Simple bridging ligands assemble two actinide metal cations into narrow dinuclear metallacycles that can trap the diatom while electrons from an externally bound group 1 metal, and protons or silanes, are added, enabling dinitrogen to be functionalized with modest but catalytic yields of six equivalents of secondary silylamine per molecule at ambient temperature and pressure.

Publication types

  • Research Support, Non-U.S. Gov't