ma301797w_si_001.pdf (971.31 kB)
Mechanistic Insight into Catalyst-Transfer Polymerization of Unusual Anion-Radical Naphthalene Diimide Monomers: An Observation of Ni(0) Intermediates
journal contribution
posted on 2012-10-09, 00:00 authored by Volodymyr Senkovskyy, Roman Tkachov, Hartmut Komber, Andreas John, Jens-Uwe Sommer, Anton KiriyNi-catalyzed polymerization of anion-radical complexes
formed upon mixing of 2,6-bis(2-bromothien-5-yl)naphthalene-1,4,5,8-tetracarboxylic-N,N′-bis(2-octyldodecyl) diimide and activated Zn
powder was investigated. We provide experimental evidence that the
polymerization involves the chain-growth mechanism and proceeds via
Ni(0) complexes which were previously proposed to be key intermediates
in other chain-growth catalyst-transfer polycondensations (CTPs),
such as Kumada CTP of thiophenic monomers. DFT calculations predict
a remarkable stability of the naphthalene diimide-based Ni(0) complexes.
A plausible polymerization mechanism is proposed.