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wangxh1984

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Recent reports have described
the placement of substituents onto R-diimine ligands and
their effect on the ¦Ò-donating ability to Pd(II) and thus the Lewis
acidity of the metal.26,27 In response, we carried out an investigation
of the polymerization behavior of a series of Pd(II) R-diimine
catalysts bearing substituents in the para-aryl position on the
ligand aromatic rings.28 We discovered that this substitution was
able to perturb the metal electronics in a regular manner, as
evidenced by the remarkably linear correlation observed in the
stretching frequencies of the corresponding carbonyl complexes.
Furthermore, several trends were observed in the physical properties
of the resulting polymers. The introduction of substituents
of increasing electron-donating ability led to catalysts that
afforded polymers of higher molecular weight, slightly reduced
branching density, and a corresponding shift toward less dendritic
polymer topologies. In the case of copolymerizations with
methyl acrylate, a clear and pronounced trend of increasing
acrylate incorporation ratio and overall tolerance to polar functionality
was also observed over the range of substitution explored.

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