The Pentagonal-Pyramidal Hexamethylbenzene Dication

Many Shades of Coordination Chemistry at Carbon

Johannes E.M.N. Klein, Remco W.A. Havenith, Gerald Knizia

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

A recent report on the crystal structure of the pentagonal-pyramidal hexamethylbenzene dication C6(CH3)6 2+ by Malischewski and Seppelt [Angew. Chem. Int. Ed. 2017, 56, 368] confirmed the structural proposal made in the first report of this compound in 1973 by Hogeveen and Kwant [Tetrahedron Lett. 1973, 14, 1665]. The widespread attention that this compound quickly gained led us to reinvestigate its electronic structure. On the basis of intrinsic bond orbital analysis, effective oxidation state analysis, ring current analysis, and comparison with well-established coordination complexes, it is demonstrated that the central carbon atom behaves like a transition metal. The central (apical) carbon atom, although best described as a highly Lewis-acidic carbon atom coordinated with an anionic cyclopentadienyl ligand, is also capable of acting as an electron-pair donor to a formal CH3 + group. The different roles of coordination chemistry are discussed.

Original languageEnglish (US)
Pages (from-to)12340-12345
Number of pages6
JournalChemistry - A European Journal
Volume24
Issue number47
DOIs
StatePublished - Aug 22 2018

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Carbon
Atoms
Coordination Complexes
Electronic structure
Transition metals
Crystal structure
Ligands
Oxidation
Electrons
hexamethylbenzene

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

Cite this

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abstract = "A recent report on the crystal structure of the pentagonal-pyramidal hexamethylbenzene dication C6(CH3)6 2+ by Malischewski and Seppelt [Angew. Chem. Int. Ed. 2017, 56, 368] confirmed the structural proposal made in the first report of this compound in 1973 by Hogeveen and Kwant [Tetrahedron Lett. 1973, 14, 1665]. The widespread attention that this compound quickly gained led us to reinvestigate its electronic structure. On the basis of intrinsic bond orbital analysis, effective oxidation state analysis, ring current analysis, and comparison with well-established coordination complexes, it is demonstrated that the central carbon atom behaves like a transition metal. The central (apical) carbon atom, although best described as a highly Lewis-acidic carbon atom coordinated with an anionic cyclopentadienyl ligand, is also capable of acting as an electron-pair donor to a formal CH3 + group. The different roles of coordination chemistry are discussed.",
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The Pentagonal-Pyramidal Hexamethylbenzene Dication : Many Shades of Coordination Chemistry at Carbon. / Klein, Johannes E.M.N.; Havenith, Remco W.A.; Knizia, Gerald.

In: Chemistry - A European Journal, Vol. 24, No. 47, 22.08.2018, p. 12340-12345.

Research output: Contribution to journalArticle

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