The stoichiometric reactivity of a β-diketiminato (BDI) magnesium silanide towards a variety of organic isocyanates has been assessed. While the primary outcome of reactions of t-BuNCO, DippNCO and CyNCO was the production of β-diketiminato magnesium siloxide adducts of the isonitrile resulting from isocyanate deoxygenation, analogous treatment with i-PrNCO led to multiple products, four of which have been positively identified. Although the specificity of this latter reaction was hampered by competitive isocycanate addition at the γ-methine carbon of the BDI supporting ligand, the identification of [{i-PrNCO}CH{(Me)CNDipp}Mg{Me₂PhSi}C(O)Ni-Pr]₆ provided corroborative evidence for the likely generation of sila-amidate intermediates in all four reactions under study. The formation of [{Me₂PhSi}C(O)NR]⁻ anions as the most likely initial species formed en route to isonitrile and siloxide formation was, therefore, validated by a computational density functional theory (DFT) study.