Reactivity of tetrel functionalized heptapnictogen clusters towards heteroallenes

Despite being known for decades, the solution-state molecular chemistry of heptapnictogen ([Pn₇]^3-; Pn = P, As) clusters is not well established. Here we study heavy element derivatives of tetrel functionalized heptapnictogen clusters towards heteroallene capture, specifically isocyanates, an isothiocyanate and CO₂ are probed. Clusters (Me₃Ge)₃P₇ (1), (Et₃Ge)₃P₇ (2), (Bu₃Sn)₃P₇ (3), and (Me₃Si)₃As₇ (4) were all found to capture isocyanates between all three of their tetrel-pnictogen bonds. In the case of phenyl isocyanate insertion, tetrel coordination at the isocyanate nitrogen atoms is preferred, while in the case of p-toluenesulfonyl isocyanate insertion, tetrel coordination at oxygen is preferred. Furthermore, the reaction of (Me₃Si)₃P₇ with CO₂ gave NMR spectra consistent with the capture of the greenhouse gas. Heteroallene insertion at these clusters was also studied using density functional theory.