In this article, we explore theoretical validations of experimental findings pertaining to the classical corner-capping reactions of a commercially available heptaisobutyltrisilanol cage to mono-substituted phenylhepta(isobutyl)-POSS cages. Additionally, the process of opening a fully condensed cage is tracked to assess the possibility of isolating and separating the resulting isomers. The corner-capping reactions of potential silanotriols, both as monomers and dimers, and the impact of these structural motifs on their closing to bifunctional POSS cages are also investigated. Our studies highlight that analyzing experimental results alone, without incorporating complex theoretical investigations, does not offer a clear understanding of the reactions involving multiple simultaneously reacting substrates, which may also undergo further transformations, potentially complicating the conventional pathways of classic corner-opening/capping reactions.