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Nonstoichiometric Stille Coupling Polycondensation via an Intramolecular Pd(0) Catalyst Transfer Using Excess Phthalimide Monomer
Author(s) -
Terayama Kosuke,
Goto Eisuke,
Higashihara Tomoya
Publication year - 2018
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201800175
Subject(s) - phthalimide , stille reaction , polymer chemistry , monomer , chemistry , thiophene , intramolecular force , catalysis , polymerization , condensation polymer , coupling reaction , polymer , photochemistry , organic chemistry
Nonstoichiometric polycondensations via Stille coupling reactions are successfully used to obtain high‐molecular‐weight π‐conjugated polymers using 2,5‐bis(trimethylstannyl)thiophene and a dibromo phthalimide monomer, N ‐hexyldecyl‐3,6‐dibromophthalimide ( 2 ), in excess from 1:1 to 1:10. The intramolecular Pd(0) catalyst transfer on 2 substituted at the polymer terminal occurs as suggested by the model reaction between 2‐(tributylstannyl)thiophene and an equimolar amount of N ‐octyl‐3,6‐dibromophthalimide ( 4 ), and the reaction generates only the disubstituted compound and excess 4 in an almost 1:1 ratio. The effect of the structures of the ligands and monomers on the polymerization under nonstoichiometric conditions is investigated to elucidate the criteria for the successful intramolecular catalyst transfer. The combination of the imide structure and an electron‐rich ligand is important for promoting the catalyst transfer.