Controlled Pd(0)/t-Bu3P-Catalyzed Suzuki Cross-Coupling Polymerization of AB-Type Monomers with ArPd(t-Bu3P)X or Pd2(dba)3/t-Bu3P/ArX as the Initiator

2015 
Controlled Pd(0)/t-Bu3P-catalyzed Suzuki cross-coupling polymerizations of AB-type monomers via the chain-growth mechanism with an ArPd(t-Bu3P)I complex as the initiator are described. ArPd(t-Bu3P)I complexes, either prepurified or generated in situ from Pd2(dba)3/t-Bu3P/ArI (dba = dibenzylideneacetone) without separation/purification, were found to be efficient initiators in general for the controlled Suzuki cross-coupling polymerization, with narrow polydispersity indexes (PDIs) of 1.13–1.35 being observed. The Pd2(dba)3/t-Bu3P/p-BrC6H4I combination was identified as a highly robust initiator system, with PDIs of ≤1.20 in general and as low as 1.13 being obtained. Higher number-average molecular weights (Mn) were achieved without a significant increase in the PDI (from 1.14 for a polymer with a Mn = 9500 to 1.20 for a polymer with Mn = 31 400) by using a smaller amount of the Pd2(dba)3/t-Bu3P/p-BrC6H4I initiator in the polymerization.
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