Dinitrogen complexation and reduction at low-valent calcium

Science. 2021 Mar 12;371(6534):1125-1128. doi: 10.1126/science.abf2374.

Abstract

Here we report that attempted preparation of low-valent CaI complexes in the form of LCa-CaL (where L is a bulky β-diketiminate ligand) under dinitrogen (N2) atmosphere led to isolation of LCa(N2)CaL, which was characterized crystallographically. The N2 2- anion in this complex reacted in most cases as a very potent two-electron donor. Therefore, LCa(N2)CaL acts as a synthon for the low-valent CaI complex LCa-CaL, which was the target of our studies. The N2 2- anion could also be protonated to diazene (N2H2) that disproportionated to hydrazine and N2 The role of Ca d orbitals for N2 activation is discussed.

Publication types

  • Research Support, Non-U.S. Gov't