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Reductive Benzylation of Dimetallo Hexaaryl[70]Fullerenes on the Equatorial Region
Author(s) -
Fujita Takeshi,
Matsuo Yutaka,
Nakamura Eiichi
Publication year - 2010
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200900651
Subject(s) - fullerene , chemistry , yield (engineering) , bromide , ionic bonding , fullerene chemistry , metal , hexa , electrochemistry , ruthenium , medicinal chemistry , ion , crystallography , inorganic chemistry , organic chemistry , materials science , catalysis , electrode , metallurgy
Dianions of dimetallic hexa(organo)[70]fullerene [(C 5 R 5 ) 2 Ru 2 C 70 Ar 6 ] 2− (R=H, Me; Ar=Ph, 4‐MeC 6 H 4 , 4‐ t BuC 6 H 4 ) react with benzylic bromide to yield the dibenzylated product dimetallic octa(organo)[70]fullerene (C 5 R 5 ) 2 Ru 2 C 70 Ar 6 (CH 2 Ar′) 2 (Ar′=Ph, 4‐MeO 2 CC 6 H 4 ), where the benzylic groups are attached to the equatorial belt region of [70]fullerene; this region is generally considered to be rather unreactive. This unusual structure was unambiguously determined by X‐ray crystallography. Theoretical studies on the electronic properties of the monoanionic intermediate indicated that the highest spin density resides on the two carbon atoms in the belt region; one of them then couples with a benzylic radical to yield the octa(organo)fullerene product after ionic substitution of the fullerene anion with a benzylic bromide. Electrochemical analysis of the hexa(organo) and octa(organo) ruthenium complexes suggests that the modification of the belt region does not affect the electronic communication between the two metal centers.