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Mechanistic Insight into Catalyst-Transfer Polymerization of Unusual Anion-Radical Naphthalene Diimide Monomers: An Observation of Ni(0) Intermediates

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journal contribution
posted on 09.10.2012, 00:00 by Volodymyr Senkovskyy, Roman Tkachov, Hartmut Komber, Andreas John, Jens-Uwe Sommer, Anton Kiriy
Ni-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.