Modern concepts and methods in the chemistry of polyhedral metallasiloxanes

•New approaches to polyhedral metallasiloxanes are reviewed. Specific nature of each route is emphasized.•Prominent sensibility of structures of polyhedral metallasiloxanes toward steric factors, ligand surrounding and complexation is described.•Connection points between polyhedral metallasiloxanes, classical siloxanes, polyoxometalates and coordination polymers are marked out.

The traditional and recent synthetic approaches to polyhedral metallasiloxanes (PHMSs) of different types are reviewed to demonstrate that each strategy yields a PHMS with a specific structure, which is typical of the particular synthetic approach selected. The factors governing the structures and transformations of PHMSs are analyzed, including examples of the formation of supramolecular aggregations of PHMSs.