Insertion of carbon monoxide into transition-metal-acyl bonds to form. cap alpha. -ketoacyl complexes

Journal Article · Wed Dec 23 04:00:00 EST 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00260a031· OSTI ID:7004774

Sheridan, J B; Han, S; Geoffroy, G L

Migratory insertion of CO into transition-metal-alkyl bonds to form acyl ligands is one of the most studied of all transition-metal organometallic reactions. In contrast, the insertion of a second CO into a metal-acyl bond to form an ..cap alpha..-ketoacyl ligand has never been observed, even though a number of important double carbonylation reactions could involve such a transformation. However, the only mechanistically studied double carbonylation catalyst has been shown to form ..cap alpha..-ketoamide products not by CO insertion into a metal-acyl bond but by reductive-coupling of two acyl ligands. Indeed, all previous studies have led to the general conclusion that insertion of CO into a metal-acyl bond is not a likely reaction. They have now discovered methodology that allows this chemistry to be accomplished by a novel oxidation/NO addition reaction sequence. Reported herein are the first examples of the formal insertion of CO into metal-acyl bonds to form ..cap alpha..-ketoacyl ligands.

• Research Organization: Pennsylvania State Univ., University Park (USA)
• OSTI ID: 7004774
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:26; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL BONDS
CHEMICAL REACTIONS
DATA
EXPERIMENTAL DATA
INFORMATION
LIGANDS
MANGANESE COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
TRANSITION ELEMENT COMPOUNDS