8: Synthesis, Structure and Catalytic Application of Cage Metallasilsesquioxanes
Silsesquioxanes (RSiO1.5) have been widely used as building units of a diverse range of hybrid organic–inorganic materials, such as the cage-like metallasilsesquioxanes (CLMSs), which display a variety of molecular architectures encompassing homo- or heterometallic polynuclear cores. These compounds exhibit interesting magnetic and photophysical properties and have found several applications in the materials science field (as flame-retardant agents and nanobuilding blocks for the design of nanoparticles, membranes and anode materials). Moreover, their catalytic properties have attracted significant attention from the academic community.
This chapter aims to discuss the several synthetic approaches to CLMSs and their role as (pre)catalysts in the homogeneous oxidative functionalization of different classes of organic compounds, namely: direct oxidation of linear and cyclic alkanes, benzene and secondary alcohols and tandem oxidation or amidation of benzyl alcohol with primary and secondary amines to yield benzamides.
We would like to dedicate this chapter to a pioneer of metallasilsesquioxane chemistry Dr. M. M. Levitsky (1938–2020).
