New dicationic and monocationic palladium complexes with 2,2'-bipyridine ligands bearing perfluorinated ponytails have been prepared and used as catalysts for CO/4-tert-butylstyrene (TBS) and CO/styrene (ST) copolymerization in supercritical carbon dioxide (scCO2) and in CO2-expanded liquids. Best catalytic performances were achieved carrying out the copolymerization in carbon dioxide expanded substrates in the presence of 2,2,2-trifluoroethanol (TFE). The dicationic systems with 5,5’-substituted ligands [Pd(N-N)2][X]2 generated the most active and productive catalysts with up to 532 g copolymer CP/g Pd•h for CO/TBS and led to polyketones with high molecular weight and narrow polydispersity (molecular weight up to Mw = 692000 for CO/ST; Mw/Mn = 1.2-3.3). MALDI-TOF mass spectrometry analysis of copolymer end groups revealed that the main initiation and termination steps involved the insertion of the alkene into the Pd-H bond and the -H-elimination on the Pd-alkyl bond, respectively.
