Synthesis, characterization and catalytic behaviors of water-soluble phosphine-sulfonato nickel methyl complexes bearing PEG-amine labile ligand

Linear, high molecular weight polyethylene from a discrete, mononuclear phosphinoarenesulfonate complex of nickel(ii)

“…Replacing PPh 3 by a weaker s-donor ligand such as DMSO or an amine also improves the catalytic activity, leading to turnover frequencies as high as 10 6 h À1 without the need for a scavenger. [18][19][20] However, there is no improvement in the molecular weight of the polyethylene. Base-free [PO]Ni(II) complexes with Z 3 -benzyl or Z 3 -allyl ligands were reported to produce polyethylene with very slightly increased molecular weights (1300 o M n o 2,100 g mol À1 ), at the expense of lower activities.…”

Oligomerization of ethylene promoted by methylaluminoxane activated arylchalcogenyl‐sulfonate nickel(II) complexes

“…Different results have been reported for phosphine‐sulfonate nickel complexes that catalyzes ethylene to oligoethylenes or low molecular weight polyethylenes. [ 16,18–20,23,24 ] This contrasting result might be associate to the low steric demanding of the phenylselenyl‐sulfonate ligand L1 , which promotes an increase in the β‐H elimination and/or chain transfer rate, thus producing lighter oligomers.…”

Synthesis and Applications in Catalysis of Metal Complexes with Chelating Phosphinosulfonate Ligands

“…72,112 [Ru(2a)(H 2 O) 2 ], which contains two diphenylphosphinobenzenesulfonate ligands coordinated to a ruthenium(II) center, proved to be an efficient ethylene polymerization catalyst in the presence of an excess of methylaluminoxane, and the resulting polymer showed a high degree of crosslinking, which contrasts with the results obtained with the previous palladium catalysts. 72,112 [Ru(2a)(H 2 O) 2 ], which contains two diphenylphosphinobenzenesulfonate ligands coordinated to a ruthenium(II) center, proved to be an efficient ethylene polymerization catalyst in the presence of an excess of methylaluminoxane, and the resulting polymer showed a high degree of crosslinking, which contrasts with the results obtained with the previous palladium catalysts.…”

“…[60][61][62] Since the seminal applications in copolymerization, it was shown that the combination of various phosphinoarylsulfonic acids with [Pd(dba) 3 ] generated active species for these transformations. 58,71,72 A recent one-pot approach to synthesize [NiMe(5e)(2,6-lutidine)] involving the formation of nickel chloride intermediates, which resulted from insertion of allyl chloride into [NiH(P^O)(lutidine)] species was reported by Nozaki (Scheme 3.26). 40 Neutral metallic-pair complexes featuring nickel phenoxyimine associated to palladium phosphinosulfonate have also been recently reported (Scheme 3.23).…”