Preparation of densely polymer backbones in a controlled and living fashion is a long-standing challenge in polymer chemistry. Transition metal-initiated carbene polymerization offers a potentially versatile and powerful strategy to accomplish this goal. However, controlled and living polymerization of carbenes or carbene surrogates has few precedents. We discovered novel transition metal-based initiators—(π-allyl)palladium carboxylate dimers—which polymerize ethyl diazoacetate in a controlled and quasi-living manner, with nearly quantitative yields, degrees of polymerization &gt;100, molecular weight dispersities of 1.2–1.4, and well-defined, diversifiable chain ends. This method also enables the preparation of novel block copolymers that undergo microphase segregation. The combination of experimental and theoretical mechanistic analyses supports a new dinuclear mechanism for this process.

Controlled and quasi-living carbene polymerization initiated by dinuclear palladium complexes

2019 Fall National Meeting

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