The (pi-allyl)palladium complex bearing an sp2-hybridized phosphorus ligand (DPCB-OMe: 1,2-bis(4-methoxyphenyl)-3,4-bis[(2,4,6-tri-tert-butylphenyl)phosphinidene]cyclobutene) efficiently catalyzes direct conversion of allylic alcohols in the absence of activating agents of alcohols such as Lewis acids. N-Allylation of aniline proceeds at room temperature to afford monoallylated anilines in 90-97% yields. C-Allylation of active methylene compounds is also successful at 50 degrees C using a catalytic amount of pyridine as a base, giving monoallylation products in 85-95% yields. The catalytic mechanism involving hydrido- and (pi-allyl)palladium intermediates has been proposed on the basis of stoichiometric examinations using model compounds of presumed intermediates.

Room‐temperature hydroamination of 1,3‐dienes with aniline [Eq. (1)] is efficiently catalyzed by cationic η3‐allyl palladium complexes, prepared by treating [{(η3‐allyl)PdCl}2] with 1,2‐diaryl‐3,4‐bis[(2,4,6‐tri‐tert‐butylphenyl)phosphinidene]cyclobutenes and AgOTf in CH2Cl2; Ar=2,4,6‐tri‐tert‐butylphenyl.

A cationic methylpalladium complex bearing a diphosphinidenecyclobutene ligand generated by the treatment of the corresponding dimethyl complex 1 with H(OEt2)2[BAr4] (Ar=3,5‐(CF3)2C6H3), exhibits good catalytic activity for ethylene polymerization in solution (up to 128 kg h−1 (mol cat.)−1). The catalyst is thermally stable and promotes the polymerization even at 100 °C without notable decomposition.

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