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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Methylplatinum triflate coordinated with 1,2-diphenyl-3,4-bis[(2,4,6-tri-t-butylphenyl)phosphinidene]cyclobutene serves as a highly selective catalyst for dehydrogenative silylation of ketones with HSiMe2Ph in the presence of pyridine as a co-catalyst, giving silyl enol ethers in high yields.

Tp Me2 Rh(coe)(MeCN) (1) (Tp Me2 ) hydrotris(3,5-dimethylpyrazolyl)borato, coe ) cyclooctene) has been found to readily undergo oxidative addition of allyl bromide at room temperature to give Tp Me2 Rh(σ-allyl)Br(MeCN) (4). On prolonged reaction time or heating, complex 4 is converted to the π-allyl complex Tp Me2 Rh(π-allyl)Br ( 5) with liberation of MeCN. Complex 5 exhibits high reactivity toward MeMgBr and Li[BHEt 3 ], giving Tp Me2 Rh(π-allyl)Me ( 8) and Tp Me2 Rh(π-allyl)H ( 9), respectively. Deuterium-labeling experiments using Li[BDEt 3 ] indicate that complex 9 is formed mainly by nucleophilic addition of Hto the central carbon of the π-allyl ligand, followed by β-hydrogen elimination of the resultant rhodacyclobutane intermediate. Complex 9 reacts with a variety of alkyl bromides by a radical process to afford 5 and alkanes.