Synthesis and reactivity of phosphine-arenesulfonate palladium(II) alkyl complexes that contain methoxy substituents.

Phosphine-arenesulfonate ligands that contain 1-3 methoxy substituents on the benzo linker, P(2-OMe-Ph) 2 (2-SO 3 Na-5-OMe-Ph) (Na[ 1a ]), P(2-MeO-Ph) 2 (2-SO 3 Na-4,5-(OMe) 2 -Ph) (Na[1b]) and P(2-MeO-Ph) 2 (2-SO 3 Li-3,4,5-(OMe) 3 -Ph) (Li[ 1c ]) were synthesized and isolated in 52–85% yield. Reaction of Na[ 1a,b ] and Li[ 1c ] with (COD)PdMeCl and pyridine generates the corresponding (PO)PdMe(pyridine) complexes 2a-c. 2a and 2b were isolated in crystalline form in 59% and 86% yield, respectively, while 2c decomposed during attempted isolation. 2a,b polymerize ethylene to linear polyethylene and copolymerize ethylene with vinyl fluoride (VF) to linear copolymer with ca. 0.5 mol % VF incorporation. The phosphine-arenesulfonate ligands Na[1a , b] and Li[1c] react with (COD)PdMeCl and pyridine to generate (PO)PdMe(pyridine) complexes 2a-c , which contain 1-3 methoxy groups on the benzo linker. 2a , b have been characterized by X-ray crystallography while 2c is thermally unstable. The ethylene polymerization and ethylene/vinyl-fluoride copolymerization behavior of 2a , b have been investigated. Image 1 • Phosphine-arenesulfonate ligands with OMe-substituted benzo linkers were prepared. • The corresponding (PO)PdMe(py) complexes were prepared and characterized. • These (PO)PdMe(py) complexes polymerize ethylene to linear polyethylene. • These (PO)PdMe(py) complexes copolymerize ethylene and vinyl fluoride. [ABSTRACT FROM AUTHOR]