In catalytic conversions of olefinic substrates, ‘chain walking’ of the active metal center along an alkyl chain is recognized to enable unique product microstructures and properties from simple low-cost petrochemical or renewable starting materials. In Ni(II)-salicylaldiminato complexes with N-terphenyl groups, substituents on the distal phenyl rings unexpectedly have a profound effect on the outcome of the reaction even though they are remote from the metal center (cf. Figure). Depending on their electronic nature, either hyperbranched oligomers or strictly linear high molecular weight polyethylene can be obtained (either products being provenly useful). To unravel the origin of the effect of the remote substituents, we present neutral [κ2-N,O]-Ni(II) salicylaldiminato catalysts bearing different structural motifs on the N-aryl moiety of the ligand and their polymerization behavior.

Remote substituent effects in Ni(II)-catalyzed chain growth catalysis

253rd National Meeting (2017)

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