Keen to understand the limits of this chemistry we considered the analogous reaction between 1 and thiophenes. Here we report a DFT study predicting the outcome of the addition of 1 to thiophenes. These calculations suggest that while metalation at the 2-position of thiophenes can occur by a similar pathway to furans, ring-opening in this system has a prohibitively high energy barrier. Experimental findings verify this prediction; a series of 2-aluminated thiophene compounds was isolated and characterised.