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A bench‐stable, hydroxy‐bridged α‐diimine‐Pd dimer can self‐activate to an olefin oligomerization and isomerization catalyst in the presence of substrate (see scheme). A cationic Pd‐hydride is generated principally through a Wacker oxidation of olefin to ketone, and with C4+ olefins, lesser amounts of allylic C‐H activation, β‐H transfer, and release of diene products are observed.
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