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Singly Bonded Monoadduct rather than Methanofullerene: Manipulating the Addition Pattern of Trimetallic Nitride Clusterfullerene through One Endohedral Metal Atom Substitution
Author(s) -
Wang Song,
Huang Jing,
Gao Congli,
Jin Fei,
Li Qunxiang,
Xie Suyuan,
Yang Shangfeng
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600388
Subject(s) - cyclopropane , reactivity (psychology) , adduct , derivative (finance) , endohedral fullerene , metal , chemistry , crystallography , atom (system on chip) , stereochemistry , polymer chemistry , fullerene , ring (chemistry) , organic chemistry , medicine , alternative medicine , pathology , computer science , financial economics , economics , embedded system
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) TiY 2 N@ I h ‐C 80 . Surprisingly, in contrast to the reported Bingel–Hirsch cyclopropane adducts of the analogous NCF Y 3 N@ I h ‐C 80 , the Bingel–Hirsch derivative of TiY 2 N@ I h ‐C 80 is the first singly bonded monoadduct (labeled as TiY 2 N@C 80 ‐Mono) to be reported, which was determined unambiguously by single‐crystal X‐ray crystallography. Besides, the reactivity of TiY 2 N@ I h ‐C 80 was found to be significantly improved relative to that of Y 3 N@ I h ‐C 80 . Upon substituting one endohedral yttrium (Y) atom of Y 3 N@ I h ‐C 80 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.