Controlled Pd(0)/<i>t</i>-Bu<sub>3</sub>P-Catalyzed Suzuki Cross-Coupling Polymerization of AB-Type Monomers with PhPd(<i>t</i>-Bu<sub>3</sub>P)I or Pd<sub>2</sub>(dba)<sub>3</sub>/<i>t</i>-Bu<sub>3</sub>P/ArI as the Initiator
作者:Hong-Hai Zhang、Chun-Hui Xing、Qiao-Sheng Hu
DOI:10.1021/ja302745t
日期:2012.8.15
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 Pd-2(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 Pd-2(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 (M-n) were achieved without a significant increase in the PDI (from 1.14 for a polymer with a M-n = 9500 to 1.20 for a polymer with M-n = 31 400) by using a smaller amount of the Pd-2(dba)(3)/t-Bu3P/p-BrC6H4I initiator in the polymerization.