The synthesis and characterisation of two mononuclear aluminium alkyl complexes with the general composition [Al(Me)2{Ph2P(E)N(CH2)2N(CH2CH2)2O}] (E = Se (2a); S (2b)), and two binuclear aluminium complexes, [Al(Me)2{Ph2P-(E)N(CH2)2N(CH2CH2)2O}(AlMe3)] (E = Se (3a) and S (3b)), are described. The binuclear aluminium alkyl complex 3a proved to be a proficient catalyst for the addition of simple nucleophiles to heterocumulenes, leading to the synthesis of a variety of products such as urea, biuret, isourea, isothiourea, phosphorylguanidine, and quinazolinone derivatives, in contrast to its mononuclear analogues. Complex 3a is the first example of a single competent catalyst, which is also low-cost and eco-friendly and derived from a main-group metal, under solvent-free conditions either at room temperature or mild temperatures. Complex 3a possessed a wide functional group tolerance including heteroatoms, yielding the corresponding insertion products in good quantities and with high selectivity. © 2023 The Royal Society of Chemistry.