Redox control in palladium catalyzed norbornene and alkyne polymerizationElectronic supplementary information (ESI) available. CCDC 1520292. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6qi00562d

Two palladium complexes (NHC)Pd(allyl)Cl (NHC = 1,3-Ar 2 -naphthoquinimidazolylidene, Ar = 2,6-Me 2 -C 6 H 3 , 2,6- i Pr 2 -C 6 H 3 ) bearing a redox-active naphthoquinone moiety, were prepared and characterized. Electro-chemistry cyclic voltammetry and NMR studies showed that these palladium complexes could be easily reduced and re-oxidized using CoCp 2 and [FeCp 2 ][BAF] (BAF = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) reagents. The properties of these neutral and reduced palladium complexes in norbornene, 5-norbornene-2-yl acetate and 1-chloro-1-octyne polymerization were studied. The neutral complexes were active in all of these polymerization reactions in the presence of Na[BAF]. In contrast, the reduced analogues showed very low activity under the same conditions. As such, switchable polymerization could be realized in this catalytic system. Switchable polymerization of norbornene, 5-norbornene-2-yl acetate and 1-chloro-1-octyne could be realized by using two palladium complexes (NHC)Pd(allyl)Cl (NHC = 1,3-Ar 2 -naphthoquinimidazolylidene, Ar = 2,6-Me 2 -C 6 H 3 , 2,6- i Pr 2 -C 6 H 3 ) bearing a redox-active naphthoquinone moiety.