Cobalt−Dinitrogen Complexes with Weakened N−N Bonds

Abstract

Reported N(2) complexes of cobalt do not have substantial weakening of the N-N bond. Using diketiminate ligands to enforce three-coordinate geometries, we have synthesized several novel CoNNCo complexes. In formally univalent complexes, cobalt is poorer than iron at weakening the N-N bond, but in formally zerovalent complexes, cobalt and iron give similar N-N weakening. The weakening is due to cobalt-to-N(2) pi-backbonding, and potassium cations pull more electron density into N(2). These results show that the low coordination number of a trigonal-planar geometry is impetus enough to make even the electronegative cobalt weaken the N-N bond of N(2).