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

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.

Rahm, Martin,1982Chalmers tekniska högskola,Chalmers University of Technology(Swepub:cth)rahmma (författare)
Haiges, RalfUniversity of Southern California (författare)
Christe, Karl O.University of Southern California (författare)
University of Southern CaliforniaChalmers tekniska högskola (creator_code:org_t)

Av författaren/redakt...: Belanger-Chabot, ...; Rahm, Martin, 19 ...; Haiges, Ralf; Christe, Karl O.

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