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

1,2-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 energy 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 1751 cm-1 is much weaker than in typical linear diaryl iminoboranes.