Dinitrogen Activation by Dihydrogen and Quaternary Cluster Anions AuNbBO - : Nb- and B-Mediated N 2 Activation and Au-Assisted Nitrogen Transfer.

Nitrogen fixation and hydrogenation are important issues in chemistry and industry. Herein, we used mass spectrometry and quantum chemical calculations to identify the quaternary AuNbBO - anions that can efficiently activate N 2 and H 2 to form imido (or amido) units in the products AuNbBON 2 H 2 - under thermal collision conditions. In these reactions, Nb and B atoms work in synergy to dissociate N 2 and the Au atom acts as a reducing agent, which facilitates the removal of one activated N atom for the following hydrogenation process; generation of three-centered, two-electron bonds facilitates N 2 activation and N transformation. This study shows that the noble metal-assisted early transition metal boronyl cluster is highly reactive to facilitate thermal N-N and H-H bond cleavage, and NH (or NH 2 ) and NBO units, which are important intermediates in N 2 hydrogenation reactions, are formed. These findings may provide insight into the design of new catalysts for the synthesis of NH 3 from N 2 and H 2 .