3,3-Diethyl-and 3,3-dibenzyl-1,2-diferrocenylcyclopropenes

Org Biomol Chem. 2003 Dec 21;1(24):4458-64. doi: 10.1039/b307408k.

Abstract

Reactions of 2,3-diferrocenylcyclopropenone 1 with ethyl- and benzylmagnesium chlorides afford 3,3-diethyl-and 3,3-dibenzyl- 1,2-diferrocenylcyclopropenes 2 and 3, respectively, and products of nucleophilic opening of the three-membered ring resulting from the addition of RMgCl to the carbonyl group, viz., saturated ketones(4,5-diferrocenylheptan-3-ones 4a,b and 3,4-diferrocenyl-1,5-diphenylpentan-2-ones 5a,b as ca. 3: 1 mixtures of two diastereomers) and other products. The spatial structures of compounds 2 and 4a were established by X-ray diffraction analysis of single crystals. Protonation of the cyclopropenes 2 and 3 with tetrafluoroboric acid at -40 degrees C yields the corresponding 3,3-dialkyl-1 ,2-diferrocenylcyclopropylium tetrafluoroborates. Transformation of the latter into diferrocenylallylic cations upon increasing the temperature to 20 degrees C and their eprotonation under the action of N,N-dimethylaniline were studied. Electrochemical investigation of 1 and 2 shows that in both complexes the cyclopropene spacer allows electronic communication between the two outer ferrocenyl groups, this being notably greater for 2 than for 1.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Crystallography, X-Ray
  • Cyclopentanes / chemical synthesis*
  • Cyclopentanes / chemistry
  • Cyclopropanes / chemical synthesis*
  • Cyclopropanes / chemistry
  • Electrochemistry
  • Ferrous Compounds / chemical synthesis*
  • Ferrous Compounds / chemistry
  • Magnesium / chemistry
  • Models, Chemical
  • Molecular Structure
  • Organometallic Compounds / chemical synthesis
  • Organometallic Compounds / chemistry
  • Spectrophotometry / methods

Substances

  • 3,3-dibenzyl-1,2-diferrocenylcyclopropene
  • 3,3-diethyl-1,2-diferrocenylcyclopropene
  • Cyclopentanes
  • Cyclopropanes
  • Ferrous Compounds
  • Organometallic Compounds
  • Magnesium