Kinetics and Mechanism of the Reactions of Bis(acetylacetonato)-palladium(II) with Alkylamines

Article abstract of DOI:10.1246/bcsj.53.1577

The reactions of bis(acetylacetonato)palladium(II), Pd(acac)2, with alkylamines (L) such as butyl-, cyclohexyl-, diethyl-, and dipropylamines in methanol to afford (acac) obey the usual two-term rate law, rate=(k₀ + k₁)).On the other hand, the rate of reaction of Pd(acac)2 with diethylamine in THF and benzene is expressed by rate = (k₁ + k₂).A mechanism is proposed which presumes the hydrogen bonding interaction of Pd(acac)2 with methanol and amine.Intermediacy of Pd(acac)(acac-C³)L in these reactions was denied on the basis of the kinetic studies, and the carbon-bonded complex was concluded to be produced via (acac).The equilibrium constants for the reactions, Pd(acac)2 + 2Et2NH<*>(acac) and Pd(acac)(acac-C³)(Et2NH) + Et2NH<*(acac were determined in dichloromethane and methanol.