Facile oxidative homocoupling of benzenes to the respective biphenyls is ef
fected under moderate conditions, using air or oxygen in the presence of ca
talytic PdCl2 and AcOH/AcONa as solvent. The fast regeneration of the activ
e Pd2+ species is accomplished by combining several oxygen-binding catalyst
s, such as Zr(IV), Mn(II), and Co(II) acetates. In this way, it is possible
to increase the content of active oxygen in solution so that the rate of c
atalyst regeneration is faster than the rate of aggregation of the "spent c
atalyst", Pd(0), to palladium black. The effects of various process paramet
ers are studied and some mechanistic implications are discussed.