Coordination chemistry at carbon

Nat Chem. 2009 Jul;1(4):295-301. doi: 10.1038/nchem.248. Epub 2009 Jun 14.

Abstract

Electron-rich allenes and heterocumulenes are commonly described by the regular notations of organic chemistry. Following on from published results and recent computational studies, we present here a host of crystallographic and reactivity data, as well as theoretical results, that indicate a highly non-canonical bonding situation in many members of this series. These must actually be interpreted as coordination compounds, in which carbon serves as a 'central atom' that interacts with its 'ligand sphere' via donor-acceptor bonds, even if these internal ligands themselves are carbon based. This captodative description is not limited to compounds that supposedly comprise a carbon(0) centre, a peculiar oxidation state that can be probed experimentally by geminal diauration. As the available data suggest that this unconventional interpretation of C-C and C-X bonds is more generally applicable than previously anticipated, it may well affect our understanding of organic chemistry in general.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Carbon / chemistry*
  • Electrons
  • Ligands
  • Methane / analogs & derivatives
  • Methane / chemistry
  • Molecular Structure
  • Nitriles / chemistry
  • Organic Chemicals / chemistry*
  • Oxidation-Reduction
  • Oxygen / chemistry
  • Phosphoranes / chemistry

Substances

  • Ligands
  • Nitriles
  • Organic Chemicals
  • Phosphoranes
  • carbene
  • Carbon
  • Methane
  • Oxygen

Associated data

  • PubChem-Substance/58098217
  • PubChem-Substance/58098218
  • PubChem-Substance/58098219
  • PubChem-Substance/58098220
  • PubChem-Substance/58098221
  • PubChem-Substance/58098222
  • PubChem-Substance/58098223
  • PubChem-Substance/58098224
  • PubChem-Substance/58098225
  • PubChem-Substance/58098226
  • PubChem-Substance/58098227
  • PubChem-Substance/58098228