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Facile successive insertion of carbon monoxide and strained alkenes has been observed for both neutral Pd(R)X(Ar-BIAN) and cationic [Pd(R)(MeCN)(Ar-BIAN)]SO 3 CF 3 complexes, i.e., complexes containing the rigid bidentate nitrogen ligands bis(arylimino)acenaphthene (Ar-BIAN; Ar=p-MeOC 6 H 4 (p-An), p-MeC 6 H 4 (p-Tol), o,o'-i-Pr 2 C 6 H 3 ), leading to the formation of new multiple insertion products of the type Pd{CH(R'CH(R')C(O)CH(R')CH(R')C(O0)R}X(Ar-BIAN). It appears that the rigidly chelating Ar-BIAN ligands have an activating effect on the insertion of CO and alkenes in palladium-carbon bonds as compared to other (bidentate) phosphorus and nitrogen ligands and a stabilizing effect on the Pd-acyl and Pd-alkyl complexes formed

journal of the american chemical society

Rigid bidentate nitrogen ligands in organometallic chemistry and homogeneous catalysis. 3. Insertion of carbon monoxide and alkenes into palladium-carbon bonds of complexes containing rigid bidentate nitrogen ligands: the first example of isolated complexes in stepwise successive insertion reactions on the way to polyketones