Pincer-ligated PdII and PtII dicationic complexes efficiently generate cations from 1,5- and 1,6-dienes. These transient cations can be selectively trapped with heteroatoms, alkenes, and through pinacol rearrangements. For example, trienyl-phenol 1 is converted into tetracyclic 2 in high yield and diastereomeric ratio (see scheme).