The vibrational spectra of complexes of Δ2-tetrazaborolines

Morris, John H.

doi:10.1016/0022-1902(74)80450-1

Cited by 3 publications

(1 citation statement)

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“…The formation of tetrazaboroles ,− is a representative example of the classical reactivity of iminoboranes, which are BN-isosteres of alkynes. In this chemistry, extensively explored by Paetzold et al, iminoboranes can be obtained by thermolysis of boron azides and can be treated (or trapped) with organic azides to yield tetrazaboroles. ,,,− ,− , Although well established, the tetrazaborole chemistry has yielded little structural data. ,, …”

Section: Resultsmentioning

confidence: 99%

Synthesis of Complex Boron–Nitrogen Heterocycles Comprising Borylated Triazenes and Tetrazenes Under Mild Conditions

et al. 2019

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The reactions of organic azides with diaryl(dihalo)diboranes(4) were explored, resulting in the observation of a number of surprising reactivity patterns. The reaction of phenyl azide with 1,2-diaryl-1,2-dihalodiboranes(4) resulted in the formation of five-membered rings comprising diboryl-triazenes with retention of the boron–boron bond, while the reaction of the peculiar 1,1-di(9-anthryl)-2,2-difluorodiborane(4) with phenyl azide yielded a six-membered ring bearing a diboryl-triazene, whereby the B–B bond was ruptured by the insertion of an arylnitrene-like reactive intermediate. Both types of heterocycles feature unprecedented connectivity patterns and are very rare examples of boryl triazenes beyond the more common 1,2,3-triazolatoboranes. They are also the product of a unique type of aryl migration from a boron center to the phenyl azide γ-nitrogen center. Lastly, the substitution of 1,2-diaryl-1,2-dihalodiboranes(4) with azide groups, using trimethylsilyl azide as the transfer reagent, yielded boryl-tetrazaboroles and diboryldiazadiboretidines (as side-products), invoking the intermediacy of the first N-boryl-substituted iminoboranes, which are BN isosteres of monoborylated alkynes. The synthetic results are complemented with mechanistic proposals derived from quantum-chemical calculations.

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