The acetato ligand of (acetato)pentaamminecobalt (III) can be removed by treatment with powerful methylating and acetylating agents. It has been shown that the reaction involves specific attack on the carbonyl atom of the ligand. The reaction has been used to prove that, in solvents of low polarity, acetylation of 18O-labeled hydroxopentaamminecobalt (III) can produce the acetato complex without breaking the metal-oxygen bond. In more polar media linkage isomerization of the acetato ligand occurs. Deacetoxylation reactions provide a convenient means of generating peiitaamminecobalt (III) complexes in which the sixth ligand is a very weak nucleophile such as tetramethylene sulfone. © 1979, American Chemical Society. All rights reserved.