Rhenium‐Mediated Conversion of Dinitrogen and Nitric Oxide to Nitrous Oxide

Abstract

Reductive splitting of N 2 is an attractive strategy towards nitrogen fixation beyond ammonia at ambient conditions. However, the resulting nitride complexes often suffer from thermodynamic overstabilization hampering functionalization. Furthermore, oxidative nitrogen atom transfer of N 2 derived nitrides remains unknown. We here report a Re IV pincer platform that mediates N 2 splitting upon chemical reduction or electrolysis with unprecedented yield. The N 2 derived Re V nitrides undergo facile nitrogen atom transfer to nitric oxide, giving nitrous oxide nearly quantitatively. Experimental and computational results indicate that outer-sphere ReN/NO radical coupling is facilitated by the activation of the nitride via initial coordination of NO.

Photoelectrochemical Conversion of Dinitrogen to Benzonitrile: Selectivity Control by Electrophile‐ versus Proton‐Coupled Electron Transfer

“…Spectroscopic and crystallographic characterization of 1 b / c support rhenium(III) in meridional octahedral coordination [15] . As a typical trend for the halide precursors, [13e, 16] cyclic voltammetry (CV) showed that the first reduction of 1 b ( E 1/2 =−1.70 V vs. FeCp 2 +/0 ) [17] and 1 c ( E 1/2 =−1.52 V) are at significantly less negative potentials with respect to 1 a ( E 1/2 =−1.84 V) [18] . At lower scan rate, the Re III/II couple becomes irreversible for all three halides, which is attributed to X − loss from [ReX 3 ( H PNP)] − as a prerequisite to N 2 activation.…”

Cooperative Dinitrogen Activation: Identifying the Push‐Pull Effects of Transition Metals and Lewis Acids in Molecular Orbital Diagrams

“…A pincer ligand system by Schneider and coworkers has proven successful in dinitrogen activation using multiple strategies with different transition metal ions [13b,34b–c,39,49] . Redox potentials were calculated using the method described by Schneider and coworkers [39] .…”

A synthetic cycle for iminophosphorane synthesis involving direct intermolecular NP bond formation on N2-derived molybdenum nitride

“…4 Very recently, Schneider reported the first example of N-N coupling after N 2 splitting to form nitrous oxide. 5 In sharp contrast, studies on N-P bond formation are exceptionally scarce. Few examples have been reported over the past few decades, most of which, are intramolecular rearrangements of the phosphine ligand in the side-on N 2 -bridged Ti 6 or U 7 complexes.…”