Premium
Crystallographic Evidence for Direct Metal–Metal Bonding in a Stable Open‐Shell La 2 @ I h ‐C 80 Derivative
Author(s) -
Bao Lipiao,
Chen Muqing,
Pan Changwang,
Yamaguchi Takahisa,
Kato Tatsuhisa,
Olmstead Marilyn M.,
Balch Alan L.,
Akasaka Takeshi,
Lu Xing
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201511930
Subject(s) - open shell , chemistry , covalent bond , metal , derivative (finance) , crystallography , shell (structure) , adduct , crystal structure , stereochemistry , materials science , organic chemistry , financial economics , economics , composite material
Endohedral metallofullerenes (EMFs) have novel structures and properties that are closely associated with the internal metallic species. Benzyl radical additions have been previously shown to form closed‐shell adducts by attaching an odd number of addends to open‐shell EMFs (such as Sc 3 C 2 @ I h ‐C 80 ) whereas an even number of groups are added to closed‐shell EMFs (for example Sc 3 N@ I h ‐C 80 ). Herein we report that benzyl radical addition to the closed‐shell La 2 @ I h ‐C 80 forms a stable, open‐shell monoadduct instead of the anticipated closed‐shell bisadduct. Single‐crystal X‐ray diffraction results show the formation of a stable radical species. In this species, the La−La distance is comparable to the theoretical value of a La−La covalent bond and is shorter than reported values for other La 2 @ I h ‐C 80 derivatives, providing unambiguous evidence for the formation of direct La−La bond.