Functionalization of N<sub>2</sub> via Formal 1,3‐Haloboration of a Tungsten(0) σ‐Dinitrogen Complex
Anna Rempel, Soren K. Mellerup, Felipe Fantuzzi, Anselm Herzog, Andrea Deißenberger, Rüdiger Bertermann, Bernd Engels, Holger Braunschweig
Abstract
Abstract Boron tribromide and aryldihaloboranes were found to undergo 1,3‐haloboration across one W−N≡N moiety of a group 6 end‐on dinitrogen complex (i.e. trans ‐[W(N 2 ) 2 (dppe) 2 ]). The N‐borylated products consist of a reduced diazenido unit sandwiched between a W II center and a trivalent boron substituent (W−N=N−BXAr), and have all been fully characterized by NMR and IR spectroscopy, elemental analysis, and single‐crystal X‐ray diffraction. Both the terminal N atom and boron center in the W−N=N−BXAr unit can be further derivatized using electrophiles and nucleophiles/Lewis bases, respectively. This mild reduction and functionalization of a weakly activated N 2 ligand with boron halides is unprecedented, and hints at the possibility of generating value‐added nitrogen compounds directly from molecular dinitrogen.