Several stable dimeric dialkylaluminum boryloxides of the formula [(mu-Mes2BO)AlR2]2 (R = Me (1), Et (2), iBu) have been prepared from dimesitylborinic acid Mes2BOH and trialkylaluminums R3Al. Compound 1 has been characterized by X-ray diffraction. These compounds exhibit diverse reactivity toward protonolytic reagents depending on the bulkiness of these reagents. Treatment of 1 with tert-butyl alcohol afforded crystalline species trans-[mu-tBuO)(Mes2BO)AlMe]2 (3), which is the first example of a mixed system containing boryloxide and alkoxide ligands together. Most surprisingly, Mes2BOH was found to undergo catalytic decomposition in the presence of [(mu-Mes2BO)AlR2]2 via the unexpected cleavage of one boron-carbon bond. The molecular structure of the decomposition product, i.e., trimesitylboroxin [MesBO]3 (4) is reported.
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