Singly Bonded Monoadduct rather than Methanofullerene: Manipulating the Addition Pattern of Trimetallic Nitride Clusterfullerene through One Endohedral Metal Atom Substitution

Bingel–Hirsch reactions of trimetallic nitride clusterfullerenes (NCFs) generally yield methanofullerene (cyclopropane) adducts instead of singly bonded derivatives, which have been reported for monometallofullerenes. Herein, we report the synthesis and characterization of the Bingel–Hirsch derivative of a mixed metal nitride clusterfullerene (MMNCF) TiY2N@Ih‐C80. Surprisingly, in contrast to the reported Bingel–Hirsch cyclopropane adducts of the analogous NCF Y3N@Ih‐C80, the Bingel–Hirsch derivative of TiY2N@Ih‐C80 is the first singly bonded monoadduct (labeled as TiY2N@C80‐Mono) to be reported, which was determined unambiguously by single‐crystal X‐ray crystallography. Besides, the reactivity of TiY2N@Ih‐C80 was found to be significantly improved relative to that of Y3N@Ih‐C80. Upon substituting one endohedral yttrium (Y) atom of Y3N@Ih‐C80 with titanium (Ti), the Bingel–Hirsch derivative changes from the cyclopropane to the singly bonded monoadduct, revealing that not only the reactivity but also the addition pattern of NCFs can be manipulated simultaneously through one endohedral metal atom substitution. Functionalized fullerenes: The first singly bonded Bingel–Hirsch derivative of trimetallic nitride clusterfullerene (NCF) is synthesized through a Bingel–Hirsch reaction of TiY2N@Ih‐C80 and diethyl bromomalonate, and its structure is unambiguously determined. Upon substituting one endohedral yttrium (Y) atom of Y3N@Ih‐C80 with titanium (Ti), the Bingel–Hirsch derivative changes from the cyclopropane to the singly bonded monoadduct.