Mechanism of the Curtius-type rearrangement in the boron series. An ab initio study of the boryinitrene (H2B–N)–iminoborane (HBNH) isomerisation

Abstract

Ab initio calculations on the model H₂BN to HBNH rearrangement suggest that the Curtius-type thermolysis of boron azide (R₂B–N₃) yielding iminoborane (RBNR) does not involve the intermediacy of borylnitrene (R₂B–N); under photochemical conditions, the later can, however, be formed from the lowest-lying triplet state of azide and does not rearrange to its more stable isomer but undergoes instead typical reactions.