Migratory-insertion of carbon monoxide into metal-acyl bonds

Gregory Geoffroy, John Sheridan, Sherri Bassner, Colleen Kelley

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10 Scopus citations

Abstract

The a-ketoacyl complex Cp’(CO)(NO)Mn-C{0}C{0}Tol, 4 (Cp’=C5H4Me), has been prepared by two independent routes involving the oxidation of the carbyne ligand in [Cp'(CO)2Mn≡CTol]+ with nitrite ion and oxidation of the anionic acyl complex [Cp(CO)2Mn-C{0}Tol]- followed by addition of NO gas. A common intermediate in both reactions is the. 17e- acyl complex [Cp(CO)2Mn-C(0)Tol]. which undergoes migratory-insertion of CO into the metal-acyl bond upon addition of NO. Aspects of the reactivity of complex 4 and its PPh3 substituted derivative 9 with electrophiles, nucleophiles, alkynes, and oxidizing agents are discussed. A surprisingly facile carbon-carbon bond cleavage of the a-ketoacyl ligand of complex 9 occurs upon either oxidation or protonation of the complex, and the a-ketoacyl ligand of complex 4 readily couples with alkynes to form metallacycles. Demetallation of the latter by treatment with acid releases vinyl-a-dione products.

Original languageEnglish (US)
Pages (from-to)1723-1729
Number of pages7
JournalPure and Applied Chemistry
Volume61
Issue number10
DOIs
StatePublished - Jan 1 1989
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

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