Direct Spectroscopic Identification of BN‐Arynes and Subtle Steric Effects on Nitrogen Fixation**

Abstract

Abstract1,2‐Azaborinines are the BN analogues of arynes through exchange of the formal CC triple bond by an isoelectronic BN bond. The BN‐arynes are an underexplored class of reactive intermediates. Dibenzo[c,e][1,2]azaborinine (10,9‐BN‐phenanthryne) 1 was inferred as reactive intermediate by trapping reactions. Here it is shown that 1 can be generated in the gas phase by thermolysis from the pyridine adduct of 9‐azido‐9‐borafluorene by cleavage of the dative bond with pyridine and dinitrogen extrusion. The ionization potential of 1 is 8.2 eV with ionization resulting from the π HOMO. Under cryogenic matrix isolation conditions, 9‐azido‐9‐borafluorene photolysis results in isomerization to the dinitrogen adduct of 1 without involvement of a triplet borylnitrene intermediate. Photochemical nitrogen extrusion from 1 ⋅ N2 is not possible and nitrogen fixation is irreversible under cryogenic conditions. In contrast, 2,4,7,9‐tetra‐tert‐butyldibenzo[c,e][1,2]azaborinine can be photogenerated from the corresponding azidoborole precursor under cryogenic matrix isolation conditions, and nitrogen fixation is precluded due to steric hindrance. The BN stretching vibration at about 1750 cm−1 is much weaker than in typical linear diaryl iminoboranes.