Affiliation:
1. School of Chemistry Monash University PO Box 23, Melbourne Victoria 3800 Australia
2. Université de Toulouse et CNRS, INSA, UPS, UMR5215, LPCNO 135 Avenue de Rangueil 31077 Toulouse France
Abstract
AbstractThe activation of dinitrogen (N2) by transition metals is central to the highly energy intensive, heterogeneous Haber–Bosch process. Considerable progress has been made towards more sustainable homogeneous activations of N2 with d‐ and f‐block metals, though little success has been had with main group metals. Here we report that the reduction of a bulky magnesium(II) amide [(TCHPNON)Mg] (TCHPNON=4,5‐bis(2,4,6‐tricyclohexylanilido)‐2,7‐diethyl‐9,9‐dimethyl‐xanthene) with 5 % w/w K/KI yields the magnesium‐N2 complex [{K(TCHPNON)Mg}2(μ‐N2)]. DFT calculations and experimental data show that the dinitrogen unit in the complex has been reduced to the N22− dianion, via a transient anionic magnesium(I) radical. The compound readily reductively activates CO, H2 and C2H4, in reactions in which it acts as a masked dimagnesium(I) diradical.
Funder
Australian Research Council
Air Force Office of Scientific Research
Alexander von Humboldt-Stiftung