2 research outputs found
Murahashi Coupling Polymerization: Nickel(II)–N-Heterocyclic Carbene Complex-Catalyzed Polycondensation of Organolithium Species of (Hetero)arenes
Revisiting
Murahashi coupling, we found that it effectively allows
polymerization of lithiated (hetero)arenes by nickel(II)-catalyzed
polycondensation. Deprotonative polymerization of 2-chloro-3-substituted
thiophene with <i>n</i>-butyllithium gave head-to-tail-type
poly(3-substituted thiophene). Poly(1,4-arylene)s were obtained by
the reaction of the corresponding dibromides through lithium–bromine
exchange. A lithiated thiophene derivative obtained via deprotonative
halogen dance also underwent polymerization to afford a bromo-substituted
polythiophene
Synthesis of Poly(3-substituted thiophene)s of Remarkably High Solubility in Hydrocarbon via Nickel-Catalyzed Deprotonative Cross-Coupling Polycondensation
Polythiophenes
bearing a siloxane moiety in a substituent at the
3-position are prepared by deprotonative polycondensation of 2-bromo-3-substituted-thiophene
with a bulky magnesium amide chloromagnesium 2,2,6,6-tetramethylpiperidine-1-yl
lithium chloride salt (TMPMgCl·LiCl) catalyzed by a nickel complex.
Deprotonation takes place at 60 °C for 1 h to form the corresponding
thiophene magnesium species, which is subjected to the polymerization
by addition of 0.1–5 mol % NiCl<sub>2</sub>(PPh<sub>3</sub>)IPr (IPr: 1,3-bis(2,6-diisopropylphenyl)imidazole-2-yl).
Polymerization proceeds in a highly regioregular manner, and the molecular
weight of the thus-obtained polymer is controllable by the ratio of
monomer feed/catalyst loading to indicate <i>M</i><sub>n</sub> of up to 280 000 with narrow molecular weight distribution.
Chlorothiophenes are also found to induce polymerization in
a deprotonative manner with TMPMgCl·LiCl or <i>n</i>BuLi (the Murahashi coupling polymerization). The obtained polymers
bearing a siloxane moiety in the substituent is revealed to be dissolved
in a hydrocarbon allowing formation of thin film from hexane