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Article

Syntheses, Structure, and Derivatization of Potassium Complexes of Penta(organo)[60]fullerene-Monoanion, -Dianion, and -Trianion into Hepta- and Octa(organo)fullerenes

Supporting Info

Yutaka Matsuo^† and Eiichi Nakamura*^†^‡

Contribution from the Nakamura Functional Carbon Cluster Project, ERATO, Japan Science and Technology Agency and Department of Chemistry, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan

J. Am. Chem. Soc., 2005, 127 (23), pp 8457–8466

DOI: 10.1021/ja050318x

Publication Date (Web): May 20, 2005

†

Nakamura Functional Carbon Cluster Project, ERATO.

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

‡

The University of Tokyo.

, nakamura@chem.s.u-tokyo.ac.jp

Abstract

Two-electron reduction of penta(organo)[60]fullerenes C₆₀Ar₅H (Ar = Ph and biphenyl) by potassium/mercury amalgam afforded potassium complexes of the corresponding open-shell radical dianions [K⁺(thf)_n]₂[C₆₀Ar₅²^-^•]. These compounds were characterized by UV−visible-near-IR and electron spin resonance spectroscopy in solution. Anaerobic crystallization of [K⁺(thf)_n]₂[C₆₀(biphenyl)₅²^-^•] that exists largely as a monomer in solution gave black crystals of its dimer [K⁺(thf)₃]₄[(biphenyl)₅C₆₀−C₆₀(biphenyl)₅⁴^-], in which the two fullerene units are connected by a C−C single bond [1.577(11) Å] as determined by X-ray diffraction. Three-electron reduction of C₆₀Ar₅H with metallic potassium gave a black−green trianion [K⁺(thf)_n]₃[C₆₀Ar₅³^-]. The reaction of the trianion with an alkyl halide RBr (R = PhCH₂ and Ph₂CH) regioselectively afforded a hepta-organofullerene C₆₀Ar₅R₂H, from which a potassium complex [K⁺(thf)_n][C₆₀(biphenyl)₅(CH₂Ph)₂^-] and a palladium complex Pd[C₆₀(biphenyl)₅(CH₂Ph)₂](π-methallyl) as well as octa-organofullerene compounds C₆₀(biphenyl)₅(CH₂Ph)₃H₂ and Ru[C₆₀(biphenyl)₅(CH₂Ph)₃H]Cp were synthesized. These compounds possess a dibenzo-fused corannulene π-electron conjugated system and are luminescent.