Abstract
Series of neutral and cationic palladium carbosilane dendritic compounds of the general formula Gn-ONNMem[Pd(X)Y] (X, Y = Cl; X = Me, Y = Cl; X = Me, Y = MeCN), containing 4 (n = 1), 8 (n = 2) or 16 (n = 3) terminal pyridylimine complexes, substituted with m methyl groups (m = 0, 2, 3), along with the corresponding monometallic counterparts (n = 0), have been synthesized. Monometallic or dendritic chloro methyl or cationic methyl palladium compounds consist of a cis/trans mixture of diastereoisomers, with compositions according to their electronic and steric features. The cationic compounds Gn-ONNMem[PdMe(MeCN)]+ are found to be active catalysts for the alternating copolymerization of CO and 4-tert-butylstyrene, producing mainly syndiotactic polyketones due to a chain-end stereocontrolled mechanism. Modification of the pyridylimine ligand framework by methyl substituents has a decisive influence on the activities of the palladium compounds. Some of them are found to retain some activity after several days...
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