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 and has undergone a tour de force of synthetic chemistry in recent years, showing a wide variety of both addition and cage-opening reactions. 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. We are continuing this work by coordinating other metals such as palladium and platinum and characterizing with single crystal x-ray diffractometry any metal-bound structures.

Coordination of metals to open cage fullerenes

ACS Fall 2021

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