Oxidative Dinuclear Addition of a Pd^I–Pd^I Moiety to Arenes: Generation of μ-η³:η³-Arene-Pd^II₂ Species

We report the oxidative dinuclear addition of a PdI–PdI bond to arenes. The oxidative dinuclear addition products, which have a bi-π-allyl-type arene dipalladium(II) structure, were obtained from [2.2]paracyclophane, anthracene, tetracene, and pentacene. A systematic study of the reaction of [Pd2(CH3CN)6][BF4]2 with benzene and polyacenes showed that the larger polyacenes, tetracene and pentacene, afforded the oxidative dinuclear addition products, while benzene, naphthalene, and anthracene gave the π-sandwich PdI–PdI complexes.