Cleavage of BN triple bonds by main group reagents.

We report two rare instances of an insertion into the strong (ca. 170 kcal mol-1) BN triple bond of iminoboranes. In the first, a silylene inserts into di-tert-butyliminoborane to form an iminosilane. In the second, the highly crowded iminoborane Ter-NB-TMP (TMP = 2,2,6,6-tetramethylpiperidyl, Ter = 2,6-(diphenylmethyl)-4-tert-butylphenyl) can be forced to react with Pip-CC-Pip (Pip = piperidyl) at 60 °C. The reaction product is the apparent result of Pip-CC insertion into the iminoborane BN bond.