With an interior void space capable of accommodating nearly any single atom on the periodic table and a host of small molecules, fullerenes have captured the interest of synthetic chemists for over 40 years. Buckminsterfullerene (C60) is the smallest and most well-studied of this class of molecules, with detailed understanding of addition and cage-opening reactions evolving through the years. Cage-opening reactions in particular have given rise to the concept of molecular surgery, wherein a fullerene is structurally modified through stepwise bond scission to yield a cage with an orifice large enough to facilitate atom, ion, or small molecule insertion. While this technique has seen tremendous progress encapsulating small covalent compounds (H2, O2, HF, CH2O, among many others), the generation of a metal-encapsulated fullerene, otherwise known as an endohedral metallofullerene, has yet evaded realization through conventional synthetic means. In recent years, we have reported silver-mediated modification and subsequent binding of the metal atom by a functionalized fullerene compound with a 12-membered orifice. Current work in this area notes the insertion of a (Ph2P)2Pt unit into the orifice of an open-cage fullerene and characterization of the resultant metal-adduct.

Open-cage fullerenes: Synthesis and use as ligands for metal coordination

ACS Spring 2022

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