Valence isomerism and rearrangements in methanofullerenes

François Diederich*, Lyle Isaacs, Douglas Philp

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

104 Scopus citations

Abstract

A PM3 computational and experimental study of the methanofullerenes 1-5 demonstrates that the electronic basis for the experimentally preferred formation of the [6,6]-closed and [6,5]-open over the [6,6]-open and [6,5]-closed isomers of methanofullerenes is the preservation of the [5]radialene-type bonding pattern found in C60 by these two structures. The [6,5]-open is the less stable of the two experimentally isolated isomers as a result of the violation of Bredt's Rule. The PM3 method locates a [6,5]-closed structure for the methanofullerenes 2-5, but not for 1. This suggests that the thermal interconversion of the [6,5]-open and [6,6]-closed isomers can only occur via a stepwise mechanism - [6,5]-open to [6,5]-closed valence isomerisation followed by a 1,5-shift - in cases where the corresponding [6,5]-closed structure is located in a local energy minimum.

Original languageEnglish (US)
Pages (from-to)391-394
Number of pages4
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number3
DOIs
StatePublished - 1994

ASJC Scopus subject areas

  • Chemistry(all)

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