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Adamantylidene Addition to M 3 N@ I h ‐C 80 (M=Sc, Lu) and Sc 3 N@ D 5 h ‐C 80 : Synthesis and Crystallographic Characterization of the [5,6]‐Open and [6,6]‐Open Adducts
Author(s) -
Yamada Michio,
Abe Tsuneyuki,
Saito Chiharu,
Yamazaki Toshiki,
Sato Satoru,
Mizorogi Naomi,
Slanina Zdenek,
Uhlík Filip,
Suzuki Mitsuaki,
Maeda Yutaka,
Lian Yongfu,
Lu Xing,
Olmstead Marilyn M.,
Balch Alan L.,
Nagase Shigeru,
Akasaka Takeshi
Publication year - 2017
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.201700049
Subject(s) - physics , materials science
Additions of adamantylidene (Ad) to M 3 N@ I h ‐C 80 (M=Sc, Lu) and Sc 3 N@ D 5 h ‐C 80 have been accomplished by photochemical reactions with 2‐adamantyl‐2,3′‐[3 H ]‐diazirine ( 1 ). In M 3 N@ I h ‐C 80 , the addition led to rupture of the [6,6]‐ or [5,6]‐bonds of the I h ‐C 80 cage, forming the [6,6]‐open fulleroid as the major isomer and the [5,6]‐open fulleroid as the minor isomer. In Sc 3 N@ D 5 h ‐C 80 , the addition also proceeded regioselectively to yield three major isomeric Ad mono‐adducts, despite the fact that there are nine types of C−C bonds in the D 5 h ‐C 80 cage. The molecular structures of the seven Ad mono‐adducts, including the positions of the encaged trimetallic nitride clusters, have been unambiguously determined through single‐crystal XRD analyses. Furthermore, results have shown that stepwise addition of Ad to Lu 3 N@ I h ‐C 80 affords several Ad bis‐adducts, two of which have been isolated and characterized. The X‐ray structure of one bis‐adduct clearly revealed that the second Ad addition took place at a [6,6]‐bond close to an endohedral metal atom. Theoretical calculations have also been performed to rationalize the regioselectivity.