η5-Cyclohexadienyltricarbonylchromium(0) Complexes from Addition of Carbon Nucleophiles to η6-Benzenetricarbonylchromium(0). Formation, Chemical and Spectroscopic Features, and X-ray Diffraction Analysis

M. F. Semmelhack, H. T. Hall, R. Farina, M. Yoshifuji, G. Clark, T. Bargar, K. Hirotsu, J. Clardy

Research output: Contribution to journalArticle

188 Scopus citations

Abstract

The addition of reactive carbanions to η6-benzenetricarbonylchromium(0) produced η5-(6-alkylcyclohexadienyl)tri-carbonylchromium(O) anion complexes, as the lithium salts. Reaction with a variety of oxidizing agents (iodine, cerium(lV), oxygen) removes the hydrogen from C-6 and detaches the Cr(CO)3 unit, to produce a substituted arene. Reaction with electrophiles (potential hydride acceptors) leads to cleavage of the carbon-carbon bond at C-6 with regeneration of η6-benzenetricar-bonylchromium(O). Solution spectral (1H NMR, IR) data are consistent with an η5-cyclohexadienyl structure. X-ray diffraction analysis on the crystalline adduct of η6-benzenetricarbonylchroinium(0) and 2-lithio-1,3-dithane defines the mode of addition (exo), the deformation (38.6°) of C-6 from the plane of carbons 1-5 in the cyclohexadienyl Iigand. and the preferred conformation of the Cr(CO)3 unit.

Original languageEnglish (US)
Pages (from-to)3535-3544
Number of pages10
JournalJournal of the American Chemical Society
Volume101
Issue number13
DOIs
StatePublished - Jun 1 1979
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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