Regiospecific coordination of tert-butylfulleride ion and 1,4-dicyclopropyltropylium ion. Synthesis of a dialkyldihydrofullerene having a heterolytically dissociative carbon-carbon {sigma} bond

Journal Article · Fri Mar 24 04:00:00 EST 1995 · Journal of Organic Chemistry

DOI:https://doi.org/10.1021/jo00111a006· OSTI ID:198126

Kitagawa, Toshikazu; Tanaka, Toru; Takata, Yuki ^[1]

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1. Kyoto Univ., (Japan); and others

The high electron affinity of fullerene (C{sub 60}) suggests that this important structure is a framework of highly stabilized carbanions. Recent studies of the controlled addition of organolithium and Grignard reagents to C{sub 60} demonstrated the formation of monosubstituted fulleride ions (RC{sub 60}{sup {minus}}) in high yields. Their regiospecific protonation to form 1-R-1,2-dihydrofullerenes as thermodynamically-controlled products has suggested that stepwise introduction of two different alkyl groups into distinct positions of the C{sub 60} framework can be achieved by using RC{sub 60}{sup {minus}} as a nucleophile. The reported high stability of t-BuC{sub 60}{sup {minus}} (1{sup {minus}}) toward electrophiles prompted the authors to synthesize new ionically-dissociative hydrocarbons by the carbocation-carbanion coordination of 1{sup {minus}} and highly stabilized hydrocarbon cations. Here, the authors report the synthesis of a disubstituted dihydro-fullerene 3 in isomerically pure form by the reaction of tert-butylfulleride ion (1{sup {minus}}), generated by deprotonation of t-BuC{sub 60}H, with 1,4-dicyclopropyltropylium ion (2{sup +}) and its reversible heterolysis to regenerate 1{sup {minus}} and 2{sup +} in highly polar solvents.

• Sponsoring Organization: USDOE
• OSTI ID: 198126
• Journal Information: Journal of Organic Chemistry, Journal Name: Journal of Organic Chemistry Journal Issue: 6 Vol. 60; ISSN 0022-3263; ISSN JOCEAH
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
ANIONS
CHEMICAL PREPARATION
FULLERENES