Interaction of Palladium(II) Acetate with Sodium and Lithium Acetate in Acetic Acid

Abstract
Palladium(II) acetate in acetic acid in the absence of acetate ion exists as the trimeric species Pd3(OAc)6. The reaction of the trimer with NaOAc or LiOAc at 25° was not instantaneous. Spectral studies on fully equilibrated systems indicated the first equilibria involved transformation of trimer to dimer[Formula: see text]with K32 = 7.77 × 104 M−5 and K′32 = 1.76 × 102 M−5. The kinetics of the slow transformation of trimer to dimer was studied. The reaction has the rate expression: rate = [Pd3(OAc)6] (k + k′[MOAc]) (M = Li or Na). This rate expression is consistent with substitution processes suggesting the slow step of the reaction is the SN2 attack of solvent or acetate on a Pd(II)–acetate bond to break one of the acetate bridges.In the NaOAc system conversion of trimer to dimer was complete at 0.2 M NaOAc. Further addition of NaOAc caused the dimer to be converted to monomer.[Formula: see text]

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