ConspectusPlastics materials are a vital component of modern technologies. They are applied, e.g., in construction, transportation, communication, water supply, or health care. Consequently, polyolefins-the most important plastics by scale-are produced in vast amounts by catalytic polymerization. Effective and selective as the catalysts used may be, their high sensitivity toward any polar compounds limits these methods to hydrocarbon reaction media and monomers like ethylene and propylene, respectively. This can be overcome by less oxophilic late transition metal catalysts, and here particularly neutral nickel(II) catalysts have seen major advances in the past few years. They stand out due to being capable of aqueous catalytic polymerizations. Aqueous polymerizations are benign processes that advantageously yield polymers in the form of particles. Moreover, these catalysts can incorporate polar monomers like acrylates, a realm previously restricted to noble metal catalysts. The introduction of polar moieties can induce properties like compatibility with metals or fibers in high performance composite materials or a desirable degradability.This Account provides a personal account of developments in the past decade. Prior findings are outlined briefly as a background. Aqueous polymerizations afford unique polyethylene morphologies as a result of the unusual underlying particle growth mechanism. Polymer single crystals are formed, which can be composed of a single ultrahigh molecular weight chain. This represents a completely disentangled state of such extremely long polymer chains, which has been long sought-after in order to overcome the difficult processing of high performance ultrahigh molecular weight materials. A key prerequisite for this approach and utilization of these catalysts, in general, is control of polymer branching and molecular weight. This is achieved via remote substituents on the Ni(II)-chelating ligand. Despite their distal position to the active site, weak secondary interactions control whether branching and chain transfer pathways compete very effectively with chain growth or are suppressed entirely. This provides access to hyperbranched oligomers, on the one hand, and enables living polymerizations to strictly linear high molecular weight polymer, on the other hand. Other advanced catalysts provide linear copolymers with in-chain polar monomer repeat units for the first time with non-noble metal active sites. Mechanistic studies further revealed that for copolymerizations with polar vinyl monomers the decisive limiting factor is irreversible termination reactions with neutral Ni(II) catalysts, rather than the well-recognized reversible blocking of coordination sites by the polar functional groups found for other types of catalysts. The mechanistic picture also implies the possibility of free-radical pathways, and their role in the formation of desirable polymer end groups and polymer blends is now being recognized. The area of neutral Ni(II) catalysts has progressed significantly in the entire range from fundamental mechanistic understanding, catalyst performance, and previously inaccessible polymer microstructures, and it is moving forward to materials through unique concepts. The unprecedented ability to incorporate functional groups into linear crystalline polyethylene also provides perspectives for much needed polyolefin materials that will not persist in the natural environment for several decades but that can be degraded by virtue of low levels of functional groups.

Perfluoroaromatic molecules have been studied intensively as versatile electron-poor pi systems. We demonstrate the use of pentafluorophenyl substituents in remote positions of Ni(II) salicylaldiminato catalysts for ethylene polymerization. With their strongly electron-withdrawing character, high molecular weights of M-n > 10(5) g/mol and simultaneously low degrees of branching are accessible due to an efficient suppression of beta-hydride elimination. This can be ascribed to suppressed nickel-aryl interactions and reduced electron densities at the metal center, as concluded from X-ray crystal structure analysis and electrochemical studies. The pentafluorophenyl-substituted catalyst is stable under aqueous conditions for direct polymerization to dispersions of well-defined nanocrystals.

Abstract In various nickel(II) salicylaldiminato ethylene polymerization catalysts, which are a versatile mechanistic probe for substituent effects, longer perfluoroalkyl groups exert a strong effect on catalytic activities and polymer microstructures compared to the trifluoromethyl group. This effect is accounted for by a reduced electron density on the active sites, and is also supported by electrochemical studies. Thus, β‐hydride elimination, the key step of chain transfer and branching pathways, is disfavored while chain‐growth rates are enhanced. This enhancement occurs to an extent that enables living polymerizations in aqueous systems to afford ultra‐high‐molecular‐weight polyethylene for various chelating salicylaldimine motifs. These findings are mechanistically instructive as well as practically useful for illustrating the potential of perfluoroalkyl groups in catalyst design.

The preparation of polymer nanoparticles with a uniform size and shape, beyond spheres, is an unresolved problem. Here we report a living aqueous catalytic polymerization, resulting in particles grown by a single active site and composed of a single ultra high molecular weight polyethylene (UHMWPE) chain. The control on a molecular level (Mw/Mn = 1.1-1.2) and at the same time on a particle level (PDI < 0.05) together with the immediate deposition of the growing chain on the growing nanocrystal results in a distinct evolution of the particle morphology over time. These uniform nanocrystals are obtained as concentrated aqueous dispersions of > 10 wt-% (N ≈ 1019 particles L-1) polymer content. Key to this robust procedure to single chain nanoparticles are long-lived water-stable Ni(II) catalysts that do not undergo any chain transfer. These findings are a relevant step towards polymer materials based on nanoparticle assembly.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Theoretical studies on the overall catalytic cycle of isomerizing alkoxycarbonylation reveal the steric congestion around the diphosphine coordinated Pd-center as decisive for selectivity and productivity. The energy profile of isomerization is flat with diphosphines of variable steric bulk, but the preference for the formation of the linear Pd-alkyl species is more pronounced with sterically demanding diphosphines. CO insertion is feasible and reversible for all Pd-alkyl species studied and only little affected by the diphosphine. The overall rate-limiting step associated with the highest energetic barrier is methanolysis of the Pd-acyl species. Considering methanolysis of the linear Pd-acyl species, whose energetic barrier is lowest within all the Pd-acyl species studied, the barrier is calculated to be lower for more congesting diphosphines. Calculations indicate that energy differences of methanolysis of the linear versus branched Pd-acyls are more pronounced for more bulky diphosphines, due to involvement of different numbers of methanol molecules in the transition state. Experimental studies under pressure reactor conditions showed a faster conversion of shorter chain olefin substrates, but virtually no effect of the double bond position within the substrate. Compared to higher olefins, ethylene carbonylation under identical conditions is much faster, likely due not just to the occurrence of reactive linear acyls exclusively but also to an intrinsically favorable insertion reactivity of the olefin. The alcoholysis reaction is slowed down for higher alcohols, evidenced by pressure reactor and NMR studies. Multiple unsaturated fatty acids were observed to form a terminal Pd-allyl species upon reaction with the catalytically active Pd-hydride species. This process and further carbonylation are slow compared to isomerizing methoxycarbonylation of monounsaturated fatty acids, but selective.