Dinitrogen reactivity with rhenium pincer complexes

Leveraging the selectivity of molecular electrocatalysts may facilitate the development of a sustainable alternative to existing methods for ammonia synthesis. Inspired by recent advances in rhenium chemistry, we prepared a new series of complexes that exhibit novel reactivity with dinitrogen. In this work, we show that a rhenium(III) pincer complex can bind dinitrogen upon loss of an auxiliary ligand. Data from X-ray crystallography demonstrate the first example of an N₂ bridged rhenium(III) dimer. Reduction causes the dinitrogen ligand to split yielding a rhenium(V) nitride product. This system serves as an opportunity to synthesize dinitrogen derived N-containing products and to study the electrochemical reactivity of rhenium and dinitrogen.