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Functionalization of N2 via Formal 1,3-Haloboration of a Tungsten(0) σ-Dinitrogen Complex

Rempel, Anna, Mellerup, Soren K., Fantuzzi, Felipe, Herzog, Anselm, Deißenberger, Andrea, Bertermann, Rüdiger, Engels, Bernd, Braunschweig, Holger (2020) Functionalization of N2 via Formal 1,3-Haloboration of a Tungsten(0) σ-Dinitrogen Complex. Chemistry - A European Journal, 26 (68). pp. 16019-16027. ISSN 0947-6539. (doi:10.1002/chem.202002678) (KAR id:98543)

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(N2)2(dppe)2]). The N-borylated products consist of a reduced diazenido unit sandwiched between a WII 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 N2 ligand with boron halides is unprecedented, and hints at the possibility of generating value-added nitrogen compounds directly from molecular dinitrogen.

Item Type: Article
DOI/Identification number: 10.1002/chem.202002678
Divisions: Divisions > Division of Natural Sciences > Chemistry and Forensics
Funders: Deutsche Forschungsgemeinschaft (https://ror.org/018mejw64)
Alexander von Humboldt Foundation (https://ror.org/012kf4317)
Coordenação de Aperfeicoamento de Pessoal de Nível Superior (https://ror.org/00x0ma614)
Depositing User: Felipe Fantuzzi
Date Deposited: 30 Nov 2022 16:25 UTC
Last Modified: 04 Mar 2024 17:39 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/98543 (The current URI for this page, for reference purposes)

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