Role of Radical Species in Salicylaldiminato Ni(II) Mediated Polymer Chain Growth: A Case Study for the Migratory Insertion Polymerization of Ethylene in the Presence of Methyl Methacrylate.

To date, an inconclusive and partially contradictive picture exists on the behavior of neutral Ni(II) insertion polymerization catalysts toward methyl methacrylate (MMA). We shed light on this issue by a combination of comprehensive mechanistic NMR and EPR studies, isolation of a key Ni(I) intermediate, and pressure reactor studies with ethylene and MMA, followed by detailed polymer analysis. An interlocking mechanistic picture of an insertion and a free radical polymerization is revealed. Both polymerizations run simultaneously (25 bar ethylene, neat MMA, 70 °C); however, the chain growth cycles are independent of each other, and therefore exclusively a physical mixture of homo-PE and homo-PMMA is obtained. A Ni-C bond cleavage was excluded as a free radical source. Rather a homolytic P-C bond cleavage in the labile aryl phosphine ligand and the reaction of low-valent Ni(0/I) species with specific iodo substituted N^O (Ar-I) ligands were shown to initiate radical MMA polymerizations. Several reductive elimination decomposition pathways of catalyst precursor or active intermediates were shown to form low-valent Ni species. One of those pathways is a bimolecular reductive coupling via intermediate (N^O)Ni(I) formation. These intermediate Ni(I) species can be prevented from ultimate decomposition by capturing with organic radical sources, forming insertion polymerization active [(N^O)Ni(II)-R] species and prolonging the ethylene polymerization activity.