Abstract
The kinetics of oxidative dimerisation of styrene to 1,4-diphenyl- 1,3-butadiene in the presence of palladium(II) acetate has been studied in acetic acid containing sodium acetate with reference to the reactivity of various palladium(II) species existent in these conditions. The most reactive species is Pd 3 (OAc) 6 which does not form detectable complexes with styrene. Dimeric species, Na 2Pd 2(OAc) 6, is the next, and, in this case, reaction involves intermediate π-complex formation. The monomeric species, Na 2Pd(OAc) 4, is unreactive. Another type of monomeric species, Pd(OAc) 2 (HOAc) 2, formed at low palladium(II) concentration in the sodium acetate- free system, is also unreactive in oxidation reaction but forms intensively absorbing π-complexes with styrene. The role of π-complexes and reaction mechanism is discussed assuming the rate determining φ-vinyl complex formation, by direct electrophilic substitution.
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