Deoximation of Oxime O-Acetates, Oximes, and Oxime Ethers by Nonacarbonyldiiron or Pentacarbonyliron. An Electronic Effect for the N–O Bond Cleavage

Abstract The reaction of [Fe2(CO)9] or [Fe(CO)5] with oxime O-acetates, oximes, and oxime ethers under photoirradiation or thermal conditions undergoes deoximation to give the corresponding ketones. The oxime O-acetate was found to be the most reactive class of these compounds. A proposed mechanism involves an initial complexation of the [Fe(CO)4] species to the nitrogen atom of the oxime group, and the subsequent N–O bond cleavage to give an imido complex. Then the imido complex could collapse to the corresponding ketone via an imine intermediate in protic media.