Reductive benzylation of dimetallo hexaaryl[70]fullerenes on the equatorial region.
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-tBuC(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.
Fujita
Takeshi
T
Department of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Matsuo
Yutaka
Y
Nakamura
Eiichi
E
D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D055664:Electrochemical Techniques; D037741:Fullerenes / Q000737:chemistry*; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D012428:Ruthenium / Q000737:chemistry
D056831:Coordination Complexes; D037741:Fullerenes; C069836:fullerene C70; D012428:Ruthenium