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Functionalization of N 2 via Formal 1,3‐Haloboration of a Tungsten(0) σ‐Dinitrogen Complex
Author(s) -
Rempel Anna,
Mellerup Soren K.,
Fantuzzi Felipe,
Herzog Anselm,
Deißenberger Andrea,
Bertermann Rüdiger,
Engels Bernd,
Braunschweig Holger
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202002678
Subject(s) - chemistry , nucleophile , moiety , electrophile , substituent , boron , surface modification , medicinal chemistry , lewis acids and bases , tungsten , bromide , crystallography , polymer chemistry , stereochemistry , inorganic chemistry , organic chemistry , catalysis
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.