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

Guillaume Belanger-Chabot ; Martin Rahm (Institutionen för kemi och kemiteknik, Fysikalisk kemi) ; Ralf Haiges ; Karl O. Christe
Angew. Chem. Int. Ed. (1521-3757). Vol. 56 (2017), 36, p. 10881-10885.
[Artikel, refereegranskad vetenskaplig]

Abstract: 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.

Nyckelord: dinitramides, dinitramidoborate, high energy density materials, tautomerism, boron chemistry



Denna post skapades 2017-07-10. Senast ändrad 2017-09-14.
CPL Pubid: 250598

 

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Institutioner (Chalmers)

Institutionen för kemi och kemiteknik, Fysikalisk kemi

Ämnesområden

Oorganisk kemi

Chalmers infrastruktur