Reactivity of the α-Ketoacyl Ligand in Cp'(L)(NO)Mn-C{O{C{O{Tol with Electrophiles, Nucleophiles, and Alkynes

Sherri L. Bassner, John B. Sheridan, Colleen Kelley, Gregory L. Geoffroy

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The reactivity of the α-ketoacyl complexes Cp'(L)(NO)Mn~C{O}C{O}Tol (Cp' = C5H4Me; 1, L = CO; 2, L = PPh3) with a variety of electrophiles, nucleophiles, and alkynes has been explored. Complex 2 undergoes protonation at the α-carbonyl oxygen at low temperature to produce a hydroxy-carbene complex. This species rearranges upon warmup by breaking the carbon-carbon bond of the α-ketoacyl ligand to give 4-methylbenzaldehyde and [Cp'Mn(PPh3)(NO)(CO)]+ (6). Oxidation of complex 2 with either [Cp2Fe]+ or Ag+ also results in the formation of complex 6 along with a mixture of organic products in which TolC(O)C{O}Tol dominates. These products indicate that oxidation induces cleavage of the α-ketoacyl carbon-carbon bond to form 6 and TolC{O} radicals. Complex 1 reacts with NEt2H under photochemical conditions to give the α-ketoamide TolC(O)C{O}NEt2. Upon photolysis, complex 1 reacts with alkynes Rceee≡Cr' to form metallacycles of the type Cp(CO)(NO)Mn=CR—CR/=C(C{O}Tol)O that result from coupling of the alkyne and the α-ketoacyl ligand. The metallacycles can be demetalated by treatment with HC1 to give vinyl α-diones that are the net result of cis addition of the α-ketoacyl ligand and a proton across the alkyne triple bond.

Original languageEnglish (US)
Pages (from-to)2121-2126
Number of pages6
Issue number9
StatePublished - Sep 1 1989
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry


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