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Reactivity of a Free Aluminylene towards Boron Lewis Acids: Accessing Aluminum‐Boron‐Bonded Species

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The reactivity of a free aluminylene towards boron Lewis acids is reported, which gives rise to rare Al−B-bonded species with either an Al−B electron-sharing bond or an Al→B dative bond. This work showcases the potent synthon of free aluminylenes for unusual Al species.


The reactivity of the free aluminylene [N]-Al (1) ([N]=1,8-bis(3,5-di-tert-butylphenyl)-3,6-di-tert-butylcarbazolyl) towards boron Lewis acids is investigated. A facile oxidative addition reaction of 1 with Ph2BOBPh2 furnishes an exceedingly scarce example of the free alumaborane [N]-Al(BPh2)(OBPh2) (2) with an Al−B electron-sharing bond. By contrast, complexation of 1 with B(C6F5)3 and HB(C6F5)2 gives rise to the corresponding Lewis adducts [N]-Al→B(C6F5)3 (3) and [N]-Al→BH(C6F5)2 (4), respectively, with an Al→B dative bond. Crystallization of 4 in Et2O produces the adduct [N]-Al(Et2O)→BH(C6F5)2 (5). Quantum chemical calculations are carried out to understand the formation of 2 as well as the bonding situation of 3 and 5.

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