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Propadiene, 3-methyl-1,2-butadiene (DMA), and 2,4-dimethyl-2,3-pentadiene (TMA) reacted via migratory insertion with both neutral and ionic Pd(R)X(p-An-BIAN) (R = Me (1), C(O)Me (2); X = Cl (a), SO3CF3 (b)) complexes, containing the rigid nitrogen ligand bis(p-anisylimino)acenaphthene (p-An-BIAN), resulting in the novel and stable allylpalladium complexes Pd(η3-C3H4R)X(p-An-BIAN) (R = Me (3), C(O)Me (6)), Pd(η3-C5H8R)X(p-An-BIAN) (R = Me (4), C(O)Me (7)), and Pd(η3-C7H12R)X(p-An-BIAN) (R = Me (5), C(O)Me (8)), respectively (X = Cl (a), SO3CF3 (b)). The neutral complexes 6a and 7a reacted with carbon monoxide to form the acylpalladium complexes Pd(C(O)C3H4C(O)Me)Cl(p-An-BIAN) (9) and Pd(C(O)C5H8C(O)Me)Cl(p-An-BIAN) (10), respectively, while the analogous trifluoromethanesulfonate complexes 6b and 7b were completely inert toward CO. Complexes 9 and 10 reacted again with propadiene and DMA, respectively, to yield the allylpalladium complexes Pd(η3-C3H4C(O)C3H4C(O)Me)Cl(p-An-BIAN) (11) and Pd(η3-C5H8C(O)C5H8C...

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Stepwise Successive Insertion of Carbon Monoxide and Allenes into Palladium−Carbon Bonds of Complexes Containing the Rigid Bidentate Nitrogen Ligand Bis(<i>p</i>-anisylimino)acenaphthene

Stepwise Successive Insertion of Carbon Monoxide and Allenes into Palladium−Carbon Bonds of Complexes Containing the Rigid Bidentate Nitrogen Ligand Bis(p-anisylimino)acenaphthene