Dinitramidoborates, a Fascinating Case of Competing Oxygen and Nitrogen Donors and Tautomerism
Journal article, 2017

Reactions of the BH4- anion with equimolar amounts of HN(NO2)2 or of BH3*THF with K+[N(NO2)2]- produced a mono-substituted [BH3N(NO2)2]- anion which contains a B-N connected dinitramido ligand. The reaction of BH4- with two equivalents of HN(NO2)2 afforded the di-substituted borate anion consisting of two isomers, one with both nitramido ligands attached to B through N and the other one with one ligand attached through N and the other one through O. The disubstituted dinitramidoborates are marginally stable under ambient conditions, and the isomer with two N-connected ligands was characterized by its crystal structure. A tri-substituted borate was tentatively identified by NMR in the reaction of BH4- with a large excess of HN(NO2)2. All anions are highly energetic. Theoretical calculations show that the energy differences between the B-N and B-O tautomers are small, explaining the observed ease of ligand exchange.

boron chemistry

tautomerism

dinitramides

high energy density materials

dinitramidoborate

Author

Guillaume Belanger-Chabot

University of Southern California

Martin Rahm

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry

Ralf Haiges

University of Southern California

Karl O. Christe

University of Southern California

Angewandte Chemie

0044-8249 (ISSN) 1521-3757 (eISSN)

Vol. 56 36 10881-10885

Subject Categories

Inorganic Chemistry

DOI

10.1002/anie.201705396

More information

Latest update

3/10/2022